Polymerizable adamantane derivatives and process for producing the same

ABSTRACT

A compound shown by the following formula:wherein each of R1a, R2a, R3a and R4a represents a substituent selected from a non-reactive atom, a non-reactive group, a hydroxyl group and an amino group, and at least two members selected from R1a, R2a, R3a and R4a are a hydroxyl group, a carboxyl group or an amino group; is subjected to an esterification reaction or an amidation reaction with a polymerizable unsaturated compound (e.g., an alcohol, a carboxylic acid, an amine) in the presence of a catalyst comprising an element selected from the Group 3 elements, such as a samarium compound, to obtain a polymerizable adamantane derivative having at least one polymerizable unsaturated group in high yield.

This application is the national phase under 35 U.S.C. §371 of prior PCTInternational Application No. PCT/JP98/02085 which has an Internationalfiling date of May 12, 1998 which designated the United States ofAmerica.

DESCRIPTION

1. Technical Field

The present invention relates to a process for producing a polymerizableadamantane derivative useful for providing a functional polymer, acatalyst useful for synthesizing polymerizable adamantane derivatives,and the novel polymerizable adamantane derivative.

2. Background Art

Photo-curable polymers or monomers have been utilized in various fields,for example, as photosensitive resins and covering agents for opticalfibers, besides paint compositions, paints, coating agents such asprinting inks and adhesives. Among such photo-setting polymers ormonomers, polycyclic hydrocarbons [e.g., norbornene (meth)acrylate,adamantane (meth)acrylate] are useful for producing coating layers ormoldings which are excellent in optical properties, mechanicalproperties and the like.

Japanese Patent Application Laid-open No. 33350/1988 (JP-A-63-33350)[Japanese Patent Publication No. 61980/1995 (JP-B-7-61980)] proposes toproduce adamantane mono(meth)acrylate by bromating an adamantane,hydrolyzing to introduce a hydroxyl group thereto, then esterifying itby using a (meth)acrylic acid or (meth) acrylic acid halide. In theintroduction of a hydroxyl group, however, it is required that anadamantane is bromated by using a large amount (e.g., 10 mole or more)of bromine, and that a formed bromide is hydrolyzed with an expensivereagent containing silver (e.g., silver nitrate or silver sulfate) in astoichiometric excess amount [Chem. Ber., 92 1629(1959), 93226,1161(1960): J. Org. Chem., 26 2207(1961)]. Moreover, in this method,reacting at a temperature of about 100° C. for hours is required.Specifically, in this method, it is difficult to considerably improveproduction efficiencies of an adamantane mono(meth)acrylate and yields.Further, in this method, a halogen remains, which is unfavorable in viewof safe hygiene and environmental hygiene.

In the above-mentioned esterification, use of (meth)acrylic acid halide(in particular chloride) is advantageous, relative to (meth)acrylicacid, to enhance yields of the objective compounds. In a process usingacid halides such as a (meth)acrylic acid chloride, however, separationof amine hydrochloride is required because amines, as a dehydrogenhalide agent, are used together with the halides. However, theseparation of the amine hydrochloride is considerably difficult, inaddition, the separation of excess amines by distillation orrecrystallization deteriorates yields of the objective compounds.

As a process for providing an adamantandiol, Japanese Patent PublicationNo. 16621/1967 (JP-B-42-16621) discloses that adamantanediol is obtainedby allowing adamantane to react, in a concentrated acetic acid solution,by using 5-fold mole or more of chromic acid relative to adamantane. Inthis process, adamantandiol can be formed, however, a treatment ofchromium components is required. In addition, oxidation of adamantanedoes not proceed to the level of polyol bodies such as tri- or morealcohol bodies even under severer reaction conditions.

A preferred oxidation process, from the viewpoints of resources and theenvironment, is a catalytic oxidation process, which is conducted withthe direct use of molecular oxygen or air as an oxidizing agent. In page762 of the “Lecture Draft II” (1994) of 67th Spring Annual Meeting ofChemical Society of Japan and Japanese Patent Application Laid-open No.38909/1996 (JP-A-8-38909), it is disclosed that adamantane is oxidizedwith oxygen by using an oxidation catalyst comprising an imide compound(e.g., N-hydroxyphthalimide) to produce adamantanemonool.

It is conceivable that adamantane mono(meth)acrylate orpoly(meth)acrylate is formed by subjecting the adamantanemonool oradamantanepolyol produced in such manner to esterification reaction with(meth)acrylic acid or acid halide. However, since the esterificationreaction is an equilibrium reaction, and an esterification efficiency ofan alcohol body of adamantane (especially, an adamantanepolyol havingplural hydroxyl groups) is low, it is difficult to obtain adamantane(meth)acrylate (in particular, an adamantane poly(meth)acrylate havingplural (meth)acryloyl groups) in a high yield.

In the Lecture Draft II (pages 1178 and 1179) of 69th Spring AnnualMeeting of Chemical Society of Japan, it is reported that equilibratoryadvantageous amidation reaction of an ester compound having a simplestructure proceeds more efficiently, in the presence of samariumcatalyst, than in the presence of a conventional Lewis acid catalyst.

It is, therefore, an object of the present invention to provide aprocess which can inhibit admixture of an halogen component and producean adamantane derivative having at least one polymerizable unsaturatedgroup in a high yield.

It is another object of the present invention to provide a process forproducing a polymerizable adamantane derivative wherein a highly pureadamantane derivative having at least one polymerizable unsaturatedgroup may effectively be formed with high efficiency, and a catalyst forsynthesizing the polymerizable adamantane derivative.

A further object of the present invention is to provide a process forproducing a polymerizable adamantane derivative wherein a polymerizableunsaturated group may effectively be introduced to the adamantanederivative by esterification or amidation in a mild or moderatecondition, and a catalyst for synthesizing the polymerizable adamantanederivative.

It is still another object of the present invention to provide a novelpolymerizable adamantane derivative useful for providing a functionalpolymer and the like.

A still further object of the present invention is to provide apolymerizable adamantane derivative which does not have a halogencomponent substantially.

DISCLOSURE OF INVENTION

The inventors of the present invention did intensive research, andfinally found that (a) oxidation of adamantane with oxygen, in thepresence of an oxidation catalyst comprising an imide compound (e.g.,N-hydroxyphthalimide) and a specific transition metal compound, providesnot only adamantanemonool but also an adamantanepolyol in highefficiency, and (b) a highly pure adamantane derivative having at leastone polymerizable unsaturated bond is formed by conducting anesterification or amidation of the formed adamantanemonool oradamantanepolyol with a polymerizable unsaturated compound, in thepresence of a catalyst comprising a rare earth metal compound. Thepresent invention has been accomplished based on the above findings.

Thus, in the present invention, a compound shown by the followingformula (1a) (adamantane derivative):

wherein R^(1a), R^(2a), R^(3a) and R^(4a) independently represent atleast one substituent selected from a non-reactive atom, a non-reactivegroup, a hydroxyl group, a hydroxymethyl group, a carboxyl group, anamino group and a reactive group derived therefrom, and at least one ofR^(1a), R^(2a), R^(3a) and R^(4a) is a hydroxyl group, a hydroxymethylgroup a carboxyl group, an amino group or a reactive group derivedtherefrom, is subjected to esterification reaction or amidationreaction, in the presence of a catalyst comprising a compound containinga Group 3A element of the Periodic Table of Elements, with at least onecompound (polymerizable unsaturated compound (1b)) selected from analcohol having a polymerizable unsaturated bond, a carboxylic acid, anamine and a reactive derivative thereof to provide a polymerizableadamantane derivative shown by the following formula (1):

wherein R¹, R², R³ and R⁴ independently represent at least onesubstituent selected from a non-reactive atom, a non-reactive group anda polymerizable unsaturated group, and at least one of R¹, R², R³ and R⁴is a polymerizable unsaturated group; X represents a connecting groupcomprising an ester bond or an amide bond, n denotes 0 or 1, and X maybe different from each other according to R¹, R², R³ and R⁴, with theproviso that n is 0 when R¹, R², R³ or R⁴ is a non-reactive atom and anon-reactive group.

In the polymerizable adamantane derivative, the polymerizableunsaturated group usually has a polymerizable unsaturated double bond,for example, an α,β-ethylenically unsaturated double bond such as vinylgroup, isopropenyl group and allyl group.

Further, the present invention comprises a catalyst for producing apolymerizable adamantane derivative having at least one polymerizableunsaturated group, namely, a catalyst for producing the polymerizableadamantane derivative represented by the formula (1) by reacting theadamantane derivative (1a) with the polymerizable unsaturated compound(1b), and this catalyst comprises a compound containing a Group 3Aelement of the Periodic Table of Elements.

An adamantane derivative of the present invention is shown by thefollowing formula (3):

wherein R¹, R², R³ and R⁴ may be the same or different and may eachrepresent at least one substituent selected from a non-reactive atom, anon- reactive group and a polymerizable unsaturated group, and at leastone of R¹, R², R³ and R⁴ is a polymerizable unsaturated group; X denotesa —OC(═O)—group in which the left end thereof is intended to be a moietybound to an adamantane back bone; n denotes 0 or 1 with the proviso thatn denote 0 when R¹, R², R³ or R⁴ is a non-reactive atom or anon-reactive group; and when the number of the polymerizable unsaturatedgroup is one or two, at least one member selected from R¹, R², R³ and R⁴is a non-reactive group selected from the group consisting of nitrogroup, amino group which may be protected by a protective group or anN-substituted amino group which may be protected by a protective group,carboxyl group which may be protected by a protective group andhydroxymethyl group which may be protected by a protective group.

Moreover, the present invention also comprises a polymerizableadamantane derivative which is shown by the formula (1) or (3) and theamount of halogen remaining is about 70 ppm or less.

In the present specification, the term “esterification” meansesterification in a wide sense such as various reactions forming anester bond, for instance, a direct reaction of an carboxylic acid withan alcohol, a reaction of a reactive derivative of a carboxylic acid(e.g., a carboxylic acid ester, a carboxylic acid halide, a carboxylicacid anhydride) with an alcohol, and a reaction of a carboxylic acidsalt with an alkyl halide. The term “protective group” or “protectinggroup” is used in a wide sense and comprises a group derived from a freefunctional group, and it may be impossible to eliminate the protectiveor protecting group.

BEST MODE FOR CARRYING OUT THE INVENTION

In the adamantane derivative shown by the formulae (1a), (1) and (3), amethylene moiety of the adamantane back bone (e.g., 2-, 4-, 6- or8-position) may be substituted with various substituents, such as an oxogroup, a halogen atom (e.g., bromine, chlorine, fluorine), a C₁₋₄ alkylgroup (e.g., methyl group, ethyl group).

The adamantane derivative shown by the formula (1a) comprises anadamantanemonool or adamantanepolyol, adamantanemonocarboxylic acid oradamantanepolycarboxylic acid, adamantanemonoamine oradamantanepolyamine, or reactive derivatives thereof, each correspondingto the polymerizable adamantane derivative (1).

As to R^(1a), R^(2a), R^(3a) and R^(4a) of the adamantane derivative(1a) (or R¹, R², R³ and R⁴ of the polymerizable adamantane (1)), anon-reactive atom and non-reactive group is a substituent inert toesterification or amidation, and may be the same or different accordingto R^(1a) to R^(4a) (or R¹ to R⁴). Examples of a non-reactive atom andnon-reactive group include at least one substituent selected from thegroup consisting of hydrogen atom, a halogen atom, an alkyl group,hydroxyl group, carboxyl group, nitro group, amino group, anN-substituted amino group, nitrile group, hydroxymethyl group and thelike.

And the “non-reactive atom” or “non-reactive group” may be selecteddepending upon the embodiment of the esterification or amidation,provided that it is inert to esterification or amidation reaction. Forexample, in a reaction of an adamantane having a hydroxyl group and acarboxyl group with a carboxyl group-containing polymerizableunsaturated compound or derivative thereof such as (meth)acrylic acid, acarboxyl group in the an adamantane is a non-reactive group. In thereaction of the adamantane with a hydroxyl group-containingpolymerizable unsaturated compound such as 2-hydroxyethyl(meth)acrylate,a hydroxyl group in the adamantane is a non-reactive group. Further, inan adamantane having an alkoxycarbonyl group, when reacted with ahydroxyl group- or an amino group-containing polymerizable compound, forexample, a C₁₋₆alkoxy-carbonyl group (especially, a C₁₋₄alkoxy-carbonylgroup) belongs to reactive groups in certain conditions (conditions oftransesterification reaction or amidation reaction).

The halogen atoms comprise fluorine, chlorine, bromine and iodine. Alkylgroups include, for instance, C₁₋₆alkyl group such as methyl, ethyl,propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, especiallyC₁₋₄alkyl groups (among them, C₁₋₂alkyl groups).

As alkoxy groups, there may be exemplified, a C₁₋₆alkoxy group such asmethoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy,t-butoxy, specifically, a C₁₋₄alkoxy group.

Alkoxycarbonyl groups include, for example, a C₁₋₆alkoxy-carbonyl groupsuch as methokycarbonyl, ethoxycarbonyl, propoxycarbonyl,isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, s-butoxycarbonyl,t-butoxycarbonyl, particularly a C₁₋₄alkoxy-carbonyl group.

Acyloxy groups include, for instance, an aliphatic C₂₋₆acyloxy groupsuch as acetyloxy, propionyloxy, isopropionyloxy, butylyloxy,isobutylyloxy, valeryloxy, isovaleryloxy, pivaloyloxy, preferably analiphatic C₂₋₄acyloxy group.

An amino group as the non-reactive group or reactive group may be anN-substituted amino group. Examples of the N-substituted amino groupinclude a mono- or diC₁₋₆alkylamino group such as methylamino,ethylamino, propylamino, dimethylamino, diethylamino, preferably a mono-or diC₁₋₄alkylamino group.

A hydroxyl group, a hydroxymethyl group, a carboxyl group or an aminogroup as the non-reactive group or reactive group may be protected by aprotective group. Examples of a group protected by a protective groupinclude the above-mentioned alkoxy group, alkoxycarbonyl group.

As a protective group of a hydroxyl group and a hydroxymethyl group,there may be exemplified the above-mentioned alkyl groups (i.e.,C₁₋₆alkyl groups, preferably C₁₋₄alkyl groups), cycloalkyl groups (e.g.,cyclohexyl group), aryl groups (e.g., 2,4-dinitrophenyl group), aralkylgroups (e.g., benzyl group, 2,6-dichlorobenzyl group, 2-nitrobenzylgroup, a benzyl group which may have a substituent such astriphenylmethyl group), tetrahydropyranyl group, non-polymerizable acylgroups [e.g., an aliphatic acyl groups such as acetyl, propionyl,isopropionyl, butylyl, isovaleryl, preferably aliphatic C₂₋₆acyl groups,especially aliphatic C₂₋₄acyl groups, aromatic acyl groups such asbenzoyl group (especially aromatic C₇₋₁₃acyl groups), alicyclic acylgroups such as cyclohexyl carbonyl group], the above-mentionedalkoxy-carbonyl groups (e.g., C₁₋₆alkoxycarbonyl groups),aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group), carbamoylgroups which may have a substituent such as a C₁₋₆alkyl group, aC₆₋₁₄aryl group (e.g., carbamoyl, methylcarbamoyl, ethylcarbamoyl,phenylcarbamoyl groups), diC₁₋₄alkylphosphynothioyl groups,diarylphosphynothioyl groups. Preferred protective groups of hydroxylgroup and hydroxymethyl group include alkyl groups, non-polymerizableacyl groups (in particular, aliphatic acyl groups), alkoxycarbonylgroups, carbamoyl groups which may have a substituent and the like.

A protective group for amino group comprises those exemplified in theitem of the protective group for hydroxyl group, for example, t-butylgroup, an aralkyl group, a non-polymerizable acyl group, analkoxycarbonyl group, an aralkyloxycarbonyl group, adialkylphosphinothioyl group, a diarylphosphinothioyl group. A preferredprotective group for amino group comprises, for example, a saturatedC₂₋₆aliphatic acyl group (particularly a saturated C₂₋₄aliphatic acylgroup), a C₇₋₁₃aromatic acyl group, a C₁₋₆alkoxy-carbonyl group.

A protective group for carboxyl group includes, for example, the aboveexemplified alkoxy group (e.g., a C₁₋₆alkoxy group, especially aC₁₋₄alkoxy group), a cycloalkyloxy group (e.g., cyclohexyloxy group), anaryloxy group (e.g., phenoxy group), an aralkyloxy group (e.g.,benzyloxy group), a triC₁₋₄alkylsllyloxy group, an amino group which mayhave a substituent [e.g., amino group; an N-substituted amino group suchas mono- or diC₁₋₆alkylamino group (e.g., methylamino group,dimethylamino group, ethylamino group, diethylamino group)], hydrazinogroup, an alkoxycarbonylhydrazino group (e.g., t-butoxycarbonylhydrazinogroup), an aralkyloxycarbonylhydrozino group (e.g.,benzyloxycarbonylhydrazyno group). As a preferred protective group forcarboxyl group, there may be exemplified an alkoxy group, an amino groupwhich may have a substituent.

In the adamantane derivative (1a), at least one member selected fromR^(1a), R^(2a), R^(3a) and R⁴ is at least one group selected fromhydroxyl group, hydroxymethyl group, carboxyl group, amino group, and areactive group derived from them, and such groups function as reactivegroups in esterification reaction or amidation reaction. In R^(1a),R^(2a), R^(3a) and R^(4a), species of the reactive groups may be thesame or different from each other. In a preferred embodiment, theadamantane derivative (1a) usually has about 1 to 4 hydroxyl groups orcarboxyl groups (especially hydroxyl groups) relative to 1 molecule.

In the adamantane derivative (1a), the substitution site (or moiety) ofthe reactive group is not strictly limited, but may be a methylenemoiety, and usually a methine carbon moiety of adamantane (i.e., 1-, 3-,5- or 7-position).

In the polymerizable unsaturated compound (1b), the polymerizableunsaturated group comprises, for example, a hydrocarbon group having apolymerizable double bond (e.g., an allyl-C₁₋₄alkyl group such as vinylgroup, isopropenyl group, an allyl group, an allylmethyl group; anα-alkyl group-substituted vinyl-C₁₋₄alkyl group such as 1-propenylgroup, 2-butenyl group) and a hydrocarbon group having a polymerizabletriple bond (e.g., ethynyl-C₁₋₄alkyl group such as ethynyl group,2-propynyl group). A preferred polymerizable unsaturated group has anα,β-ethylenycally unsaturated bond (e.g., vinyl group, isopropenylgroup, an allyl group, especially vinyl group or isopropenyl group).Such polymerizable unsaturated groups may be the same or different fromeach other according to R^(1a), R^(2a), R^(3a) and R^(4a).

As an alcohol having a polymerizable unsaturated bond among thepolymerizable unsaturated compounds as (1b), there may be exemplified, acompound having an unsaturated double bond [e.g., an allyl alcohol; ahydroxyalkyl (meth)acrylate (e.g., a hydroxyC₂₋₆alkyl (meth)acrylatesuch as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate,6-hydroxyhexyl (meth)acrylate); a (poly)oxyC₂₋₄alkylene glycolmono(meth)acrylate such as a diethylene glycol mono(meth)acrylate, atriethylene glycol mono(meth)acrylate, a polyethylene glycolmono(meth)acrylate, a dipropylene glycol mono(meth)acrylate, atripropylene glycol mono(meth)acrylate, a polypropylene glycolmono(meth)acrylate, a polyoxytetramethyleneglycol mono(meth)acrylate], acompound having an unsaturated triple bond [e.g., propalgyl alcohol]. Asa reactive derivative of such alcohols, there may be exemplified, anallyl halide (e.g., an allyl chloride, an allyl bromide).

As examples of a carboxylic acid having a polymerizable unsaturatedbond, there may be exemplified compounds having an unsaturated doublebond [e.g. monocarboxylic acids such as (meth)acrylic acid, crotonicacid, vinylacetic acid and allylacetic acid; polycarboxylic acids suchas maleic acid, fumaric acid and itaconic acid; and monoalkylester ofthe polycarboxylic acid], and compounds having an unsaturated triplebond [e.g. propiolic acid].

The reactive derivatives of such carboxylic acids include acidanhydrides [e.g. (meth)acrylic anhydride, maleic anhydride], compoundshaving a leaving group (e.g. a halogen atom, an alkyl group, an alkenylgroup, an alkynyl group, an aryl group, a cycloalkyl group, an aralkylgroup).

The reactive derivatives of carboxylic acids having a leaving groupinclude, for example, acid halides [e.g. (meth)acrylic chloride,(meth)acrylic bromide], carboxylic acid alkyl esters [e.g. carboxylicacid C₁₋₆alkyl esters (particularly, carboxylic acid lower C₁₋₄alkylesters) such asmethyl (meth)acrylate, ethyl (meth)acrylate, propyl(meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate andt-butyl (meth)acrylate], carboxylic acid alkenylesters [e.g. carboxylicacid C₂₋₆alkenyl esters (particularly, carboxylic acid C₂₋₆alkenylesters, among them, specifically, carboxylic acid C₂₋₄alkenyl esters)such as vinyl (meth)acrylate, allyl (meth)acrylate, 1-propenyl(meth)acrylate, isopropenyl (meth)acrylate, 1-butenyl (meth)acrylate,2-butenyl (meth)acrylate, 3-butenyl (meth)acrylate and 2-pentenyl(meth)acrylate], carboxylic acid alkynyl esters [e.g. carboxylic acidC₂₋₁₀alkynyl esters (particularly, carboxylic acid C₂₋₆alkynyl esters,among them, specifically carboxylic acid C₂₋₄alkynyl esters) such asethynyl (meth)acrylate and propynyl (meth)acrylate], carboxylic acidaryl esters [e.g. phenyl (meth)acrylate], carboxylic acid cycloalkylesters [e.g. carboxylic acid C₃₋₁₀cycloalkyl esters such as cyclohexyl(meth)acrylate], carboxylic acid aralkyl esters [e.g. carboxylic acidphenyl-C₁₋₄alkyl esters such as benzyl (meth)acrylate].

Examples of a preferred reactive derivative include carboxylic acidhalides, carboxylic acid lower C₁₋₆alkyl esters (particularly,C₁₋₄alkylesters), carboxylic acid C₂₋₆alkenyl esters (particularly,C₂₋₄alkenyl esters) and carboxylic acid C₂₋₆alkynyl esters(particularly, C₂₋₄alkynyl esters). Particularly, when a carboxylic acidhalide or a carboxylic acid C₂₋₆alkenyl ester is used, a correspondingpolymerizable adamantane derivative can be produced with highselectivity and yield by the exchange reaction of a leaving group whileinhibiting a side reaction such as an addition polymerization.

As examples of an amine having a polymerizable unsaturated bond, theremay be exemplified compounds having an unsaturated double bond, such asallylamine, butenylamine and diallylamine.

Examples of a preferred compound having a polymerizable unsaturated bondinclude carboxylic acids having a polymerizable unsaturated bond andreactive derivatives thereof, particularly, carboxylic acids having anα,β-ethylenically unsaturated double bond or triple bond, or reactivederivatives thereof [e.g. carboxylic halides, carboxylic acid lowerC₁₋₄alkyl esters, carboxylic acid C₂₋₄alkenyl esters]. As an organiccarboxylic acid, an organic carboxylic acid having an α,β-ethylenicallyunsaturated double bond (particularly, acrylic acid, methacrylic acid,and the like) is advantageous.

Incidentally, in the method of the present invention, the production ofan amine hydrochloride and the like can be inhibited, and when acarboxylic acid lower C₁₋₄alkyl ester or a carboxylic acid C₂₋₄alkenylester is used, contamination of the intended compound can be preventedby a halogen component. Moreover, since a compound having a low boilingpoint (e.g. the ester described above) can be used as a polymerizableunsaturated compound (1b)(a reactive component), a treatment after areaction can be conducted without difficulty, and an isolation yield canbe vastly improved.

In the present invention, an esterification reation (including anexchange reaction of a leaving group such as transesterificationreaction) or an amidation reaction of the adamantane derivative (1a)with the polymerizable unsaturated compound (1b) is carried out in thepresence of a catalyst composed of a compound comprising a Group 3element of the Periodic Table of Elements in order to enhance reactivityto obtain the polymerizable adamantane derivative with high yield.

Referring to the catalyst of the present invention composed of acompound comprising a Group 3A element of the Periodic Table ofElements, as a Group 3A element of the Periodic Table of Elements, theremay be exemplified rare earth elements [e.g. scandium, yttrium,lanthanoid-series elements (lanthanum, cerium, praseodymium, neodymium,promethium, samarium, europium, gadolinium, terbium, dysprosium,holmium, erbium, thulium, ytterbium, lutetium), actinoid series elements(e.g. actinium).

Examples of a preferred Group 3A element of the Periodic Table ofElements include rare earth elements such as scandium, yttrium andlanthanoid-series elements (e.g. samarium, gadolinium, ytterbium).Especially, samarium has a high catalytic activity.

Referring to the compound comprising a Group 3A element of the PeriodicTable of Elements, the valence of a Group 3A element of the PeriodicTable of Elements is not particularly restricted, and may be about 2 to4 valence, practically divalent or trivalent. The above-mentionedcompound comprising a Group 3A element of the Periodic Table of Elementsis not restricted provided that has a catalytic activity, and may be acompound or a complex with a metal simple substance, an inorganiccompound (e.g. a halide, an oxide, a double oxide, phosphorus compounds,a nitrogen compound) or an organic compound (e.g. an organic acid). Ahydroxide containing the above element, an oxygen acid salt, an organicacid salt, an inorganic acid salt, a halide, a coordination compound(complex) each containing the above metal element are practically used.The complex may be a π-complex such as a metallocene compound. Further,the Group 3 element-containing compound may be a composite metalcompound containing a different metal. These catalysts can be usedeither singly or in combination of two or more.

Hereinafter, taking a samarium compound for example, a component of acatalyst will be described concretely and, needless to say, a compoundcontaining other Group 3A element of the Periodic Table of Elementscorresponding to the samarium compound also can be used effectively.

The hydroxide includes, for example, a samarium (II) hydroxide, asamarium (III) hydroxide. The metal oxide includes, for example, asamarium (II) oxide, a samarium (III) oxide.

As the organic acid salt, there may be exemplified salts of organicacids such as organic carboxylic acids (e.g. monocarboxylic acids suchas formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid,propionic acid, butyric acid, valeric acid, naphthenic acid and stearicacid; polycarboxylic acids such as oxalic acid and maleic acid),oxycarboxylic acids (e.g. glycolic acid, lactic acid, malic acid,tartaric acid, citric acid), thiocyanic acids and sulfonic acids (e.g.alkylsulfonic acids such as methanesulfonic acid,trichloromethanesulfonic acid, trifluoromethanesulfonic acid andethanesulfonic acid; aryl sulfonic acids such as benzenesulfonic acidand p-toluenesulfonic acid). As the inorganic acid salt, there may beexemplified nitrates, sulfates, phosphates, carbonates and perchlorates.Concrete examples of the organic acid salt or inorganic acid salt are asamarium (II) acetate, a samarium (III) acetate, a samarium (II)trichloroacetate, a samarium (III) trichloroacetate, a samarium (II)trifluoroacetate, a samarium (III) trifluoroacetate, a samarium (II)trifluoromethanesulfate (i.e., samarium (II) triflate), a samarium (III)trifluoromethanesulfonic acid (i.e., samarium (III) triflate), asamarium (II) nitrate, a samarium (II) sulfate, a samarium (II)phosphate and a samarium (II) carbonate.

The halide includes a fluoride, a chloride, a bromide and an iodide, andthere may be exemplified a samarium (II) iodide, a samarium (III)iodide, a samarium (II) bromide, a samarium (III) bromide, a samarium(II) chloride, a samarium (III) chloride.

A ligand constituting a complex includes, for example, OH (hydroxo), analkoxy group such as methoxy, ethoxy, propoxy and butoxy group; an acylgroup such as acetyl and propionyl group; an alkoxycarbonyl group suchas methoxycarbonyl (acetato) and ethoxycarbonyl group; anacetylacetonato, a cyclopentadienyl, C₁₋₄alkyl-substitutedcyclopentadienyls (e.g. C₁₋₂alkyl-substituted cyclopentadienyls such aspentamethylcyclopentadienyl), dicyclopentadienyl, C₁₋₄alkyl-substituteddicyclopentadienyls (e.g. C₁₋₂alkyl-substituted dicyclopentadienyls suchas pentamethyldicyclopentadienyl); halogen atoms such as chlorine andbromine; CO; CN; oxygen atom; H₂O (aquo); phosphorus compounds such asphosphines (e.g. triarylphosphines such as triphenylphosphine);nitrogen-containing compounds such as NH₃ (ammine), NO, NO₂ (nitro), NO₃(nitrato), ethylenediamine, diethylenetriamine, pyridine,phenanthroline. In the complexes or complex salts, the same or differentligand may be coordinated singly or in combination.

Among the above complexes, as the samallocene-type complex, there may beexemplified a diacetylaceto-natosamarium (II), atriacetylacetonatosamarium (III), a dicyclopentadienylsamarium (II), atricyclopentadienylsamarium (III), adipentamethylcyclopentadienylsamarium (II), atripentamethylcyclopentadienylsamarium (III).

When the Group 3A element-containing compound [e.g. a divalentsamallocene-type complex having a high-electron-donativepentamethylcyclopentadienyl ligand [e.g. (C₅Me₅)₂Sm; (PMSM)], a halogencompound of samarium, or an alkoxide or a hydroxide compound ofsamarium] is used as a catalyst, not only in an amidation reaction, butalso in an esterification reaction in spite of an equilibrium reaction,the esterifaction proceeds with a higher reaction efficiency than thatof a Lewis acid catalyst or a protonic acid catalyst while inhibitingside reactions. The catalyst of the present invention is advantageousfor the production of the above polymerizable adamantane derivative (1)employing an exchange reaction of a leaving group such astransesterification reaction.

The catalyst composed of the compound comprising a Group 3A element maybe whichever of a homogeneous system or a heterogeneous system.Moreover, the catalyst may be a solid catalyst in which a catalyticcomponent supported on a support or carrier, and the catalytic componentis constituted of a Group 3A element-containing compound. As the supportor carrier, porous supports such as active carbon, zeolite, silica,silica-almina, bentonite are practically used. In the solid catalyst, asupported amount of the catalyst component is about 0.1 to 50 parts byweight of the Group 3A element-containing compound, preferably about 0.5to 30 parts by weight and more preferably about 0.1 to 20 parts byweight, relative to 100 parts by weight of the support.

The amount of the catalyst composed of the above Group 3Aelement-containing compound may be selected within a wide range. To givean example, the amount can be selected from the ranges of about 0.1 mole% to 1 equivalent, preferably 0.5 to 50 mole %, more preferably 1 to 25mole % (e.g. 5 to 20 mole %), relative to the above adamantanederivative (1a).

The aforementioned esterification or amidation reaction is advantageouswhen conducted in the presence of an oxime. The oxime may be whicheverof an aldoxime or ketoxime. Examples of the oxime are aliphatic oximessuch as 2-hexanone oxime, alicyclic oximes such as cyclo-hexanone oxime,aromatic oximes such as acetophenone oxime, benzophenone oxime andbenzyl dioxime.

The amount of the oxime can be selected within a wide range of, forexample, about 0.1 mole % to 1 equivalent, preferably 1 to 50 mole % andmore preferably 5 to 40 mole % (e.g. 5 to 30 mole %), relative to theadamantane derivative (1a).

The ratio of the polymerizable unsaturated compound (1b) to theadamantane derivative (1a) is not specifically restricted so far as notadversely affecting the production efficiency of the polymerizableadamantane derivative (1). The amount of the polymerizable unsaturatedcompound (1b) may be about 0.5 to 5 mole, preferably about 0.8 or more(e.g. about 0.8 to 5mole) and particularly about 1 mole or more (e.g.about 1 to 3 mole, particularly about 1 to 1.5 mole), relative to 1equivalent of the adamantane derivative (1a) (i.e., the weight of theadamantane derivative per hydroxyl group, carboxyl group, amino group,or reactive derivative group thereof). Since the esterification reactionis an equilibrium reaction, a larger amount of the polymerizableunsaturated compound (1b) makes the reaction more advantageous in itsprocess. However, since the catalyst of the present invention has a veryhigh catalytic activity, an excessive amount of the polymerizableunsaturated compound (1b) is unnecessary. In particular, in the reactionof a combination which is disadvantageous from the point of view ofreaction equilibrium, when the above alkenyl ester (e.g. vinyl ester)having a vinylic leaving group is used as the polymerizable unsaturatedcompound (1b), even if the compound (1b) in an amount of about 1 mole orless (e.g. about 0.4 to 1 mole, preferably about 0.5 to 1 mole) per 1equivalent of the leaving group of the adamantane derivative (1a) isused, the reaction immediately goes to completion, and good results areobtained.

In contrast to the high reaction heat produced by the conventionalmethod employing an acid halide such as (meth)acrylic chloride,according to the method of the present invention, the reaction heat islow. Therefore, even with the solvent in a small amount, the reactionproceeds smoothly and the objective compound can be produced in highyield.

The above esterification reaction or amidation reaction may be carriedout either in the presence or absence of a solvent inert to thereaction. Examples of such reactive solvent are aliphatic hydrocarbonssuch as hexane, octane; alicyclic hydrocarbons such as cyclohexane;aromatic hydrocarbons such as benzene, toluene and xylene; ketones suchas acetone, methyl ethyl ketone and methylisobutyl ketone; ethers suchas dioxane, diethyl ether and diisopropyl ether, tetrahydrofuran;non-polar protic solvents such as dimethylformamide, dimethylacetamide,N-methylpyrolidone, acetonitrile and benzonitrile; and mixed solventsthereof. As the reactive solvent, the polymerizable unsaturated compound(1b) also may be used.

Among adamantane derivatives (1a), a compound having a plurality of, forexample, hydroxyl groups or carboxyl groups has high hydrophilicity, andthe reaction system tends to be heterogeneous when the prevailingreactive solvent for esterification (e.g. hydrophobic solvents such astoluene) is used. Therefore, when the adamantane derivative having highhydrophilicity is used, as the preferred solvent, there may beexemplified hydrophilic solvents (e.g. ketones such as acetone andmethyl ethyl ketone; ethers such as dioxane, diethyl ether andtetrahydrofuran; non-polar protic solvents) and a mixed solvent of ahydrophilic solvent and a hydrophobic solvent (e.g. an aliphatic, or analicyclic or an aromatic hydrocarbon.)

Since the above reaction is an equilibrium reaction, the reaction isadvantageously accelerated when a reaction inhibitive component such asa leaving component is immediately removed from the reaction system. Theleaving component is advantageously removed when a solvent having a highboiling point (e.g. an organic solvent having a boiling point of about50 to 120° C., particularly 60 to 115° C.) or an azeotropic solvent(e.g. the above hydrocarbons) are used.

The temperature for an esterification or an amidation reaction may beselected within a range of, for example, about 0 to 150° C., preferablyabout 25 to 120° C. When the catalyst composed of the above Group 3element-containing compound is used, even under mild or moderateconditions, the polymerizable adamantane derivative can be produced withhigh efficiency. In this case, the reaction temperature may be, forexample, 0 to 150° C., preferably 10 to 100° C. and more preferably 20to 80° C. In particular, the reaction can smoothly be conducted, evenunder mild conditions of about 20 to 50° C., by using, for example, theabove organic carboxylic acid alkenyl ester as the above polymerizableunsaturated compound (1b). The reaction can be conducted under ambientpressure or reduced pressure, or under pressure (under a load).Moreover, the reaction can be effected in a conventional manner such asin a batch system, semi-batch system or continuous system.

Such reaction makes it possible to produce the polymerizable adamantanederivative represented by the aforementioned formula (1) with highefficiency.

In the polymerizable adamantane derivative (1), X is a connecting groupfor connecting an adamantane to a polymerizable unsaturated group, andcomposed of an ester bond (—COO—, —OCO—), or an amide bond (—NHCO—,—CONH—). The connecting group may be a group having an ester bond (e.g.—CH₂COO—), or a group having an amide bond. Generally, X is composed ofan ester bond.

Typical examples of the connecting group X having the abovepolymerizable unsaturated group are (meth)acryloyloxy group,(meth)acryloyloxymethyl group, (meth)acryloylamino group,(meth)acryloyloxy-C₂₋₁₀alkyloxycarbonyl group, allyloxy carbonyl group,allylamino carbonyl group.

In the aforementioned formula (1), n stands for 0 or 1, X may bedifferent according to R¹, R², R³ and R⁴. Moreover, if whichever of R¹,R², R³ and R⁴ is a non-reactive atom such as a hydrogen atom or anon-reactive group, n denotes 0.

Typical examples of the compounds represented by the aforementionedformula (1) are polymerizable adamantane derivatives having an esterbond [(meth)acrylates, e.g., 1,3-bis[(meth)acryloyloxy] adamantane,1,7-bis[(meth)acryloyloxy] adamantane, 1,3,5-tris[(meth)acryloyloxy]adamantane, 1,3,7-tris[(meth)acryloyloxy] adamantane,1,3,5,7-tetrakis[(meth)acryloyloxy] adamantane; adamantanes having a(meth)acryloyloxy-C₂₋₁₀alkyloxy group, such as1,3-bis[(2-(meth)acryloyloxyethyl)oxycarbonyl] adamantane,1,7-bis[(2-(meth)acryloyloxyethyl)oxycarbonyl] adamantane,1,3,5-tris[(2-(meth)acryloyloxyethyl)oxycarbonyl] adamantane,1,3,7-tris[(2-(meth)acryloyloxyethyl)oxycarbonyl] adamantane and1,3,5,7-tetrakis[(2-(meth)acryloyloxyehtyl)oxycarbonyl] adamantane;allyl esters, e.g., 1,3-bis(allyloxycarbonyl) adamantane,1,7-bis(allyloxycarbonyl) adamantane, 1,3,5-tris(allyloxycarbonyl)adamantane, 1,3,7-tris(allyloxycarbonyl) adamantane,1,3,5,7-tetrakis(allyloxycarbonyl) adamantane]; polymerizable adamantanederivatives having an amide bond [(meth)acrylamides, e.g.,1,3-bis[(meth)acryloylamino] adamantane, 1,7-bis[(meth)acryloylamino]adamantane, 1,3,5-tris[(meth)acryloylamino] adamantane,1,3,7-tris[(meth)acryloylamino] adamantane,1,3,5,7-tetrakis[(meth)acryloylamino] adamantane; allyl amides, e.g.,1,3-bis(allylaminocarbonyl) adamantane, 1,7-bis(allylaminocarbonyl)adamantane, 1,3,5-tris(allylaminocarbonyl) adamantane,1,3,7-tris(allylaminocarbonyl) adamantane,1,3,5,7-tetrakis(allylaminocarbonyl) adamantane]. These compounds mayhave at least one substituent selected from various substitutents, e.g.,a halogen atom, an alkyl group, a hydroxyl group which may be protectedby a protective group (e.g. hydroxyl group, an alkoxy group, an acyloxygroup, carbamoyloxy group), a carboxyl group which may be protected by aprotective group (e.g. carboxyl group, an alkoxycarbonyl group, acarbamoyl group which may have a substituent), an amino group which maybe protected by a protective group (e.g. amino group, an acyl aminogroup, an alkoxycarbonyl amino group), an N-substituted amino group, anitro group, a hydroxymethyl group which may be protected by aprotective group. The substituent may be substituted at a suitableposition in an adamantane (particularly, whichever of the 1,3,5 and 7-positions in the adamantane skeleton).

These polymerizable adamantane derivatives (1), by a conventionalmethod, can be easily separated and purified after completion of thereaction. Examples of the conventional methods are, for example,separation methods such as filtration, concentration, distillation,extraction, crystallization, recrystallization and columnchromatography, and combination methods thereof.

[Method for producing an adamantane derivative (1a)]

The adamantane derivative (1a), as a raw material of the polymerizableadamantane derivative, may be prepared by introducing at least onereactive group selected from the group consisting of a hydroxyl group, ahydroxymethyl group, a carboxyl group, an amino group and a reactivederivative group thereof to an adamantane in which R^(1a), R^(2a),R^(3a) and R^(4a) have at least one substituent selected from anon-reactive atom or a non-reactive group (hereinafter, referred tosimply as an adamantane). The number of the above substituent of theadamantane is usually about 0 to 3 per 1 molecule, and the species ofthe substituents may be different from each other according to thespecies of the adamantane derivative (1a). Further, if necessary,adamantanes of which the reactive group has a substitution rate lowerthan that of the objective compound (1a) can also be used.

As the adamantane (substrate), there may be exemplified an adamantane, ahalogen-containing adamantane (particularly, a chlorine-, orbromine-substituted adamantane), an alkyl group-containing adamantane(particularly, a C₁₋₂alkyl group-substituted adamantane), a hydroxylgroup-containing adamantane which may be protected by a protective group[e.g. a hydroxyl group-containing adamantane, an alkoxy group-containingadamantane (particularly, a C₁₋₂alkoxy group-substituted adamantane), anacyloxy group-containing adamantane, an alkoxycarbonyloxygroup-containing adamantane, a carbamoyloxy group-containing adamantanewhich may have a substituent], a carboxyl group-containing adamantanewhich may be protected by a protective group [a carboxylgroup-containing adamantane, an alkoxycarbonyl group-containingadamantane (e.g. a C₁₋₄alkoxycarbonyl group-containing adamantane), acarbamoyl group-containing adamantane which may have a substituent], anitro group-containing adamantane, an amino group-containing adamantanewhich may be protected by a protective group (e.g. an aminogroup-containing adamantane, an alkoxycarbonylamino group-containingadamantane, an acylamino group-containing adamantane), an N-substitutedamino group-containing adamantane (e.g. a C₁₋₆acylamino group-containingadamantane, a mono-, or di-C₁₋₄alkylamino group-containing adamantane),a hydroxymethyl group-containing adamantane which may be protected by aprotective group.

An adamantane may have a plurality of different species of substituents.For example, 1-methyl-3-adamantanol, 1-methyl-3-carboxyadamantane,1-methyl-3-nitroadamantane, 1-carboxy-3-adamantanol,1-nitro-3-adamantanol, 1-nitro-3-carboxyadamantane may also be used.

As an adamantane, a compound that is commercially available can also beemployed. Further, a reactive group or a substituent may be introducedto adamantanes by the following method.

[Hydroxyl group-containing adamantane derivative]

Among the adamantane derivatives represented by the aforementionedformula (1a), the compounds having a hydroxyl group can be obtained by aconventional oxidation method, e.g., oxidation method employing a nitricacid or a chromic acid, oxygen-oxidation method employing a cobalt saltas a catalyst, biochemical oxidation method. The hydroxylgroup-containing adamantane derivatives can also be obtained byintroducing a halogen atom (e.g. bromine atom), then hydrolyzing withthe use of inorganic salts such as silver nitrate, silver sulfate,whereby introducing a hydroxyl group. In a preferred method, thehydroxyl group-containing adamantane derivative can be obtained byoxidizing the substrate corresponding to the aforementioned formula (1a)with oxygen in the presence of an oxydatiqn catalyst composed of animide compound represented by the following formula (2) or of ancatalyst composed of the above imide compound (2) and a co-catalyst.

(In the formula, R¹¹ and R¹² independently represent a hydrogen atom, ahalogen atom, an alkyl group, an aryl group, a cycloalkyl group, ahydroxyl group, an alkoxy group, a carboxyl group, alkoxylcarbonylgroup, or an acyl group, or R¹¹ and R¹² may bond together to form adouble bond or an aromatic and non-aromatic ring; Y represents an oxygenatom or a hydroxyl group, and the bond between the nitrogen atom “N” and“Y” is a single bond or a double bond. m denotes an integer of 1 to 3.

[Imide compound (2)]

In the compound shown by the formula (2), a halogen atom, as thesubstituents R¹¹ and R¹², includes an iodine, a bromine, a chlorine anda fluorine atom. The alkyl group includes a straight chain or branchedchain C₁₋₁₀alkyl group such as methyl, ethyl, propyl, isopropyl, butyl,isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl and decyl. Anillustrative preferred alkyl group includes a lower C₁₋₆alkyl group, inparticular a lower C₁₋₄alkyl group. As the aryl group, there may bementioned, for instance, a phenyl group and a naphthyl group. Examplesof the cycloalkyl group include cyclopentyl, cyclohexyl, and cyclooctylgroup. The alkoxy group includes, for example, C₁₋₁₀alkoxy groups suchas methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy,pentyloxy and hexyloxy. Among them, lower C₁₋₆alkoxy group, particularlya lower C₁₋₄alkoxy group is preferable.

Examples of the alkoxycarbonyl group include C₁₋₁₀oalkoxy-carbonylgroups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl,pentyloxycarbonyl, hexyloxycarbonyl. A preferred alkoxycarbonyl groupincludes lower C₁₋₆alkoxy-carbonyl groups, particularly lowerC₁₋₄alkoxycarbonyl groups.

The acyl group includes, for instance, C₁₋₆acyl groups such as formyl,acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl and pivaloylgroup.

The substituents R¹¹ and R¹² may be the same or different from eachother. In the formula (1), R¹¹ and R¹² may bond together to form adouble bond, or an aromatic or non-aromatic ring. A preferred aromaticor non-aromatic ring may be a ring having about 5 to 12 members, inparticular about 6 to 10 members. Such a ring may be a heterocyclic ringor a condensed heterocyclic ring, and it may practically be ahydrocarbon ring. As such a ring, there may be mentioned, for instance,non-aromatic alicyclic rings (e.g., cycloalkane rings which may have asubstituent such as a cyclohexane ring, optionally substitutedcycloalkene rings such as a cyclohexene ring), non-aromatic bridged(cross-linked) rings (e.g., optionally substituted bridged hydrocarbonrings such as a 5-norbornene ring), optionally substituted aromaticrings such as a benzene ring and a naphthalene ring. The ring maypractically comprise an aromatic ring.

A preferred imide compound (2) includes compounds shown by the followingformulae.

(In the formula, R¹³ to R¹⁶ independently represent a hydrogen atom, analkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, analkoxycarbonyl group, an acyl group, a nitro group, a cyano group, anamino group or a halogen atom; R¹¹, R¹² and m have the same meanings asdefined above.)

In the substituents R¹³ to R¹⁶, the alkyl group includes alkyl groupssimilar to those exemplified above, in particular C₁₋₆alkyl groups. Thealkoxy group includes the same alkoxy groups as mentioned above, inparticular lower C₁₋₄alkoxy groups. Examples of the alkoxycarbonyl groupinclude the same alkoxycarbonyl groups as exemplified above,particularly lower C₁₋₄alkoxycarbonyl groups. As the acyl group, theremay be mentioned acyl groups similar to those mentioned above, inparticular C₁₋₆acyl groups. Examples of the halogen atom includefluorine, chlorine and bromine atoms. The substituents R¹³ to R¹⁶ maypractically be a hydrogen atom, a lower C₁₋₄alkyl group, a carboxylgroup, a nitro group or a halogen atom, respectively.

The symbol X in the formula (2) denotes an oxygen atom or a hydroxylgroup. A bond between the nitrogen atom “N” and “Y” is a single bond ora double bond. Further, m usually denotes about 1 to 3, preferably 1 or2. The imide compound shown by the formula (2) may be used singly or incombination in the oxidation reaction.

As examples of the acid anhydride corresponding to the imide compound ofthe formula (2), there may be mentioned saturated or unsaturatedaliphatic dicarboxylic acid anhydrides such as succinic anhydride,maleic anhydride, saturated or unsaturated nonaromatic cyclicpolycarboxylic acid anhydrides (alicyclic polycarboxylic anhydrides)such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride(1,2-cyclohexanedicarboxylic anhydride),1,2,3,4-cyclohexanetetracarboxylic acid 1,2-anhydride, bridged cyclicpolycarboxylic anhydrides (alicyclic polycarboxylic anhydrides) such ashetic anhydride, himic anhydride, aromatic polycarboxylic anhydridessuch as phthalic anhydride, tetrabromophthalic anhydride,tetrachlorophthalic anhydride, nitrophthalic anhydride, trimelliticanhydride, methylcyclohexenetricarboxylic anhydride, pyromelliticanhydride, mellitic anhydride, 1,8;4,5-naphthalenetetracarboxylicdianhydride.

Examples of a preferred imide compound include N-hydroxysuccinimide,N-hydroxymaleimide, N-hydroxyhexahydrophthalimide,N,N′-dihydroxycyclohexanetetracarboximide, N-hydroxyphthalimide,N-hydroxytetrabromophthalimide, N-hydroxytetrachlorophthalimide,N-hydroxyhetimide, N-hydroxyhimimide, N-hydroxytrimellitimide,N,N′-dihydroxypyromellitimide, N,N′-dihydroxynaphthalenetetracarboximideand so forth. A typically preferable compound includes an N-hydroxyimidecompound derived from an alicyclic polycarboxylic anhydride, inparticular from an aromatic polycarboxylic anhydride, such asN-hydroxyphthalimide.

The imide compound may be prepared by a conventional imidation process(a process for the formation of an imide), such as a process thatcomprises the steps of allowing a corresponding acid anhydride to reactwith hydroxylamine NH₂OH for ring-opening of an acid anhydride group,and closing the ring to form an imide.

These imide compounds have high oxidation activity, and cancatalystically accelerate the oxidation reaction of an admantane evenunder mild or moderate conditions. Further, when various species ofsubstrates are oxidized in the coexistence of the imide compound and theco-catalyst, the conversion and/or selectivity coefficient of thehydroxyl group-containing derivative is improved.

[Co-catalyst]

A co-oxidizing agent as the co-catalyst includes or comprises a metalcompound such as a compound comprising or containing a Group 2A elementof the Periodic Table of Elements (e.g., magnesium, calcium, strontium,barium), a transition metal compound, and a compound containing a Group3B element (e.g., boron B, aluminium Al) of the Periodic Table ofElements (e.g., a boron compound). These co-catalysts may be employedindependently or in combination.

As the elements of the transition metal, there may be mentioned, forinstance, Group 3A elements of the Periodic Table of Elements (e.g.,scandium Sc, yttrium Y, and lanthanoid elements such as lanthanum La,cerium Ce, samarium Sm, actinoid elements such as actinium Ac), Group 4Aelements of the Periodic Table of Elements (e.g., titanium Ti, zirconiumZr, hafnium Hf), Group 5A elements (e.g., vanadium V, niobium Nb,tantalum Ta), Group 6A elements (e.g., chromium Cr, molybdenum Mo,tungsten W), Group 7A elements (e.g., manganese Mn, technetium Tc,rhenium Re), Group 8 elements (e.g., iron Fe, ruthenium Ru, osmium Os,cobalt Co, rhodium Rh, iridium Ir, nickel Ni, palladium Pd, platinumPt), Group 1B elements (e.g., copper Cu, silver Ag, gold Au) and Group2B elements of the Periodic Table of Elements (e.g., zinc Zn, cadmiumCd).

A preferred element constituting the co-catalyst includes elements ofthe transition metals (e.g., Group 3A elements of the Periodic Table ofElements such as lanthanoid elements, actinoid elements, Group 4Aelements, Group 5A elements, Group 6A elements, Group 7A elements, Group8 elements, Group 1B elements, and Group 2B elements of the PeriodicTable of Elements) and Group 3B elements of the Periodic Table ofElements (e.g., boron compounds). In particular, high oxidizingactivities are demonstrated when the imide compound of the formula (2)is used in combination with a compound containing Group 4A elements suchas Ti and Zr; Group 5A elements such as V; Group 6A elements such as Cr,Mo and W; Group 7A elements such as Mn, Tc and Re; Group 8 elements suchas Fe, Ru, Co, Rh and Ni; or Group 1B elements such as Cu.

The species of the co-catalyst is not particularly limited as far as itcontains the element and has oxidizing property, and it may be a simplesubstance or hydroxide of a metal. The co-catalyst may practically be anoxide of a metal (a double oxide or an oxygen acid salt) comprising theelement, an organic acid salt, an inorganic acid salt, a halide, acoordinate compound (a complex) comprising the metal element, or apolyacid (a heteropolyacid, particularly an isopolyacid) or its salt.

As the boron compound, there may be mentioned, for example, a boronhydride (e.g., borane, diborane, tetraborane, pentaborane, decaborane),a boric acid (e.g., orthoboric acid, metaboric acid, tetraboric acid), aborate (e.g., a nickel borate, magnesium borate, manganese borate),boron oxides such as B₂O₃; nitrogen-containing boron compounds such asborazane, borazene, borazine, boron amide, boron imide; BF₃; BCl₃;halides such as tetrafluoroborate; esters of boric acid (e.g., methylborate, phenyl borate).

The hydroxide includes Mn(OH)₂, MnO(OH), Fe(OH)₂ and Fe(OH)₃, typicallyspeaking. Examples of the metal oxide include Sm₂O₃, TiO₂, ZrO₂, V₂O₃,V₂O₅, CrO, Cr₂O₃ MoO₃, MnO, Mn₃O₄, Mn₂O₃, MnO₂, Mn₂O₇, FeO, Fe₂O₃,Fe₃O₄, RuO₂, RuO₄, CoO, CoO₂, Co₂O₃, RhO₂, Rh₂O₃, Cu₂O₃, and so forth.As examples of the double oxide or oxygen acid salt, there may bementioned MnAl₂O₄, MnTiO₃, LaMnO₃, K₂Mn₂O₅, CaO.xMnO₂ (x=0.5, 1, 2, 3,5), manganate [e.g., manganates(V) such as Na₃MnO₄, Ba₃[MnO₄]₂;manganates(VI) such as K₂MnO₄, Na₂MnO₄, BaMnO₄; permanganates such asKMnO₄, NaMnO₄, LiMnO₄, NH₄MnO₄, CsMnO₄, AgMnO₄, Ca(MnO₄)₂, Zn(MnO₄)₂,Ba(MnO₄)₂, Mg(MnO₄)₂, Cd(MnO₄)₂].

As the organic acid salts, there may be exemplified salts with a C₂₋₂₀fatty acid such as cobalt acetate, manganese acetate, cobalt propionate,manganese propionate, cobalt naphthenate, manganese naphthenate, cobaltstearate, manganese stearate, manganese thiocyanate, and correspondingsalts of Ce, Ti, Zr, V, Cr, Mo, Fe, Ru, Ni, Pd, Cu and Zn. The inorganicacid salt includes, for instance, nitrates such as cobalt nitrate, ironnitrate, manganese nitrate, nickel nitrate, copper nitrate, andsulfates, phosphates and carbonates each corresponding to these nitrates(e.g., cobalt sulfate, iron sulfate, manganese sulfate, cobaltphosphate, iron phosphate, manganese phosphate, an iron carbonate, amanganese carbonate, iron perchlorate). As the halides, there may bementioned halides, for instance, chlorides such as SmCl₃, SmI₂, TiCl₂,ZrCl₂, ZrOCl₂, VCl₃, VOCl₂, MnCl₂, MnCl₃, FeCl₂, FeCl₃, RuCl₃, CoCl₂,RhCl₂, RhCl₃, NiCl₂, PdCl₂, PtCl₂, CuCl, CuCl₂, or fluorides, bromidesor iodides each corresponding to these chlorides (e.g., MnF₂, MnBr₂,MnF₃, FeF₂, FeF₃, FeBr₂, FeBr₃, FeI₂, CuBr, CuBr₂) and complex halidessuch as M¹MnCl₃, M¹ ₂MnCl₄, M¹ ₂MnCl₅, M¹ ₂MnCl₆, wherein M¹ representsa monovalent metal.

The ligand constituting the complex includes, for example, OH (hydroxo),alkoxy groups such as methoxy, ethoxy, propoxy, butoxy; acyl groups suchas acetyl, propionyl; alkoxycarbonyl groups such as methoxycarbonyl(acetato), ethoxycarbonyl; acetylacetonato; cyclopentadienyl group;halogen atoms such as chlorine, bromine; CO; CN; oxygen atom; H₂O(aquo), phosphorus compounds such as phosphine (e.g., triarylphosphinesuch as triphenylphosphine); nitrogen-containing compounds such as NH₃(ammine), NO, NO₂ (nitro), NO₃ (nitrato), ethylenediamine,diethylenetriamine, pyridine, phenanthroline. In the complexes orcomplex salts, the same or different ligands may be coordinated singlyor in combination.

The transition metal element and the ligand may optionally be employedin combination to form a complex. Such a complex includes, for instance,acetylacetonato complexes [e.g., acetylacetonato complex of Ce, Sm, Ti,Zr, V, Cr, Mo, Mn, Fe, Ru, Co, Ni, Cu or Zn, titanylacetylacetonatocomplex TiO(AA)₂, zirconylacetylacetonato complex ZrO(AA)₂,vanadylacetylacetonato complex VO(AA)₂], cyano complexes [e.g.,hexacyanomanganate(I), hexacyanoferrate(II)], carbonyl complexes orcyclopentadienyl complexes [e.g.,tricarbonylcyclopentadienylmanganese(I),biscyclopentadienylmanganese(II), biscyclopentadienyliron(II), Fe(CO)₅,Fe₂(CO)₉, Fe₃(CO)₁₂], nitrosyl compounds [e.g., Fe(NO)₄, Fe(CO)₂(NO)₂],thiocyanato complexes [e.g., thiocyanatocobalt, thiocyanatomanganese,thiocyanatoiron], or acetyl complexes [e.g. cobalt acetate, manganeseacetate, iron acetate, copper acetate, zirconyl acetate ZrO(OAc)₂,titanyl acetate TiO(OAc)₂, vanadyl acetate VO(OAc)₂].

The polyacid (isopolyacid or heteropolyacid) is practically at least onemember selected from Group 5A elements and Group 6A elements of thePeriodic Table of Elements, such as V (vanadic acid), Mo (molybdic acid)and W (tungstic acid), typically speaking. There is no particular limitas to the central atom, and it may be any of, for instance, Cu, Be, B,Al, Si, Ge, Sn, Ti, Th, N, P, As, Sb, V, Nb, Ta, Cr, Mo, W, S, Se, Te,Mn, I, Fe, Co, Ni, Rh, Os, Ir, Pt, or Cu. As illustrative examples ofthe heteropolyacid, there may be mentioned cobaltmolybdate,cobalttungstate, molybdenumtungstate, manganesemolybdate,manganesetungstate, manganesemolybdenumtungstate,vanadomolybdophosphate, manganesevanadiummolybdate, andmanganesevanadomolybdophosphate.

These co-catalysts may be employed independently or in combinationdepending on the species of a substrate and so forth.

As to the transition metal compound constituting of the co-catalysts,the valency of the element is not particularly restricted, and it may beabout 2 to 6 valencies. The use of a divalent transition metal compound(e.g., a divalent cobalt compound, a divalent manganese compound) as theco-catalyst enhances oxidation activity. By way of illustration, acatalytic system comprising the imide compound in combination with adivalent transition metal compound instead of a trivalent transitionmetal compound may induce an oxidized product with high selectivity andin high yield within a short period of time.

Incidentally, the use of a compound containing at least one elementselected from Group 4A elements (e.g., Ti, Zr), Group 6A elements (e.g.,Cr. Mo) and Group 7A elements (e.g., Mn) of the Periodic Table ofElements as the co-catalyst considerably inhibits the inactivation(deactivation) of the catalyst (in particular the imide compound) evenunder severe reaction conditions. Therefore, the process insuresoxidation of the substrate with oxygen or air with commercialadvantages.

Further, the use of a compound containing a Group 4A element (e.g., Ti,Zr), Group 5A element (e.g., V), Group 6A element (e.g., Cr, Mo), Group7A element (e.g., Mn) or Group 8 element (e.g., Fe, Co) of the PeriodicTable of Elements as the co-catalyst results in remarkable enhancementof the oxidizing activity and provides effective oxidation of thesubstrate. By way of an example, a catalytic system comprising, as theco-catalyst, a compound containing a Group 5A element (e.g., V), Group7A element (e.g., Mn) or Group 8 element (e.g., Co) of the PeriodicTable of Elements has high activities. Specifically, the use of acompound containing a Group 5A element (e.g., V) as a co-catalystinsures or achieves an efficient oxidation of plural sites (inparticular a methine carbon site) of a substrate and provides anadamantanepolyol to which plural hydroxyl groups are introduced. Theoxidation catalyst comprising the imide compound (2), a compoundcontaining a Group 7A element of the Periodic Table of Elements (e.g., amanganese compound), and a compound containing a Group 8 element of thePeriodic Table of Elements (e.g., an iron compound) in combination hasan improved and enhanced catalytic activities and provides an oxideeffectively and advantageously with high conversion and selectivity. Insuch complex catalyst, the ratio of the compound containing a Group 8element of the Periodic Table of Elements (the second co-catalyst) isnot particularly limited, and practically, for instance, about 0.1 to 25mole (e.g., about 0.1 to 20 mole), preferably about 0.2 to 15 mole, andmore preferably about 0.5 to 10 mole relative to one mole of thecompound containing the Group 7A element of the Periodic Table ofElements (the first co-catalyst).

Moreover, the use of the oxidation catalyst comprising the imidecompound shown by the formula (2) and a co-catalyst containing a Group1B element of the Periodic Table of Elements (e.g., Cu) considerablyenhances selectivity in the oxidation reaction and inhibits theinactivation (deactivation) of the imide compound, hence commerciallyadvantageous.

The oxidation catalyst comprising the imide compound or the oxidationcatalytic system comprising the imide compound and the co-catalyst maybe whichever of a homogeneous system or a heterogeneous system. Theoxidation catalyst or the oxidation catalytic system may be a solidcatalyst comprising a catalytic component supported on a support orcarrier. As the support, use can be practically made of porous supportssuch as activated carbon, zeolite, silica, silica-alumina, bentonite. Inthe solid catalyst, the supported amount of the catalytic component maybe about 0.1 to 50 parts by weight of the imide compound shown by theformula (2), preferably about 0.5 to 30 parts by weight and morepreferably about 1 to 20 parts by weight relative to 100 parts by weightof the support. The ratio of the co-catalyst supported on the support isabout 0.1 to 30 parts by weight, preferably about 0.5 to 25 parts byweight, and more preferably about 1 to 20 parts by weight, relative to100 parts by weight of the support.

The relative ratio of the co-catalyst to the imide compound shown by theformula (2) may be selected from a range not interfering with thereaction velocity or rate and selectivity, and may be, for example,about 0.001 to 10 mole, preferably about 0.005 to 5 mole, morepreferably about 0.01 to 3 mole and practically about 0.01 to 5 mole (inparticular about 0.001 to 1 mole).

Incidentally, as the amount of the co-catalyst increase, the activity ofthe imide compound sometimes deteriorates. Therefore, for the purpose ofmaintaining high activity of the oxidation catalytic system, theproportion of the co-catalyst is not less than an effective amount tonot more than about 0.1 mole (e.g., about 0.001 to 0.1 mole, preferablyabout 0.005 to 0.08 mole, and more preferably about 0.01 to 0.07 mole)relative to 1 mole of the imide compound.

The amount of the imide compound shown by the formula (2) in theoxidation reaction is selected from a broad range, and may for examplebe about 0.001 to 1 mole (0.01 to 100 mole %), preferably about 0.001 to0.5 mole (0.1 to 50 mole %), more preferably about 0.01 to 0.30 mole andpractically about 0.01 to 0.25 mole, relative to 1 mole of thesubstrate, typically speaking.

The amount of the co-catalyst (a co-oxidizing agent) can be suitablyselected from a range not interfering with the reactivity andselectivity, and is, for example, about 0.0001 mole (0.01 mole %) to 0.7mole (70 mole %), preferably about 0.0001 to 0.5 mole, more preferablyabout 0.001 to 0.3 mole, and practically about 0.0005 to 0.1 mole (e.g.,0.005 to 0.1 mole) relative to one mole of the substrate.

When a polyacid (an isopolyacid or a heteropolyacid) or salt thereof isused as a co-catalyst, the amount is 0.1 to 25 parts by weight,preferably 0.5 to 10 parts by weight, and more preferably 1 to 5 partsby weight relative to 100 parts by weight of the substrate.

In the oxidation reaction of adamantanes, the oxygen used in theoxidation may be active oxygen, but molecular oxygen is practicallyemployed for economical advantages. Such molecular oxygen is notspecifically limited, and use may be made of whichever of pure oxygen,or oxygen diluted with an inert gas such as nitrogen, helium, argon orcarbon dioxide. From the viewpoints of not only handling and safety butalso economy, air is preferably employed.

The amount of oxygen may be selected according to the species of anadamantane, from the range of about 0.5 mole or more (e.g., 1 mole ormore), preferably about 1 to 100 mole, and more preferably about 2 to 50mole relative to 1 mole of the substrate. The oxygen is practically usedin an excess mole relative to an adamantane. In specific, the reactionis advantageously carried out in an atmosphere containing molecularoxygen such as air or oxygen gas.

The oxidation process of the present invention is usually conducted inan organic solvent inert to the reaction. As the organic solvents, theremay be mentioned, for example, organic carboxylic acids (e.g., formicacid, acetic acid, propionic acid) or hydroxycarboxylic acids; nitrilessuch as acetonitrile, propionitrile, benzonitrile; amides such asformamide, acetamide, dimethylformamide (DMF), dimethylacetamide;alcohols such as t-butanol, t-amyl alcohol; aliphatic hydrocarbons suchas hexane, octane; aromatic hydrocarbons such as benzene; halogenatedhydrocarbons such as chloroform, dichloromethane, dichloroethane, carbontetrachloride, chlorobenzene; nitro compounds such as nitrobenzene,nitromethane, nitroethane; esters such as ethyl acetate, butyl acetate;ethers such as dimethyl ether, diethyl ether, diisopropyl ether,dioxane; and mixtures of these solvents. Use may practically be made of,as the solvent, organic acids such as acetic acid, nitriles such asacetonitrile, benzonitrile.

When the reaction is carried out in the presence of a protonic acid, theoxidation reaction may be smoothly carried out and a desired compound isobtained with high selectivity and in a high yield. As mentioned above,the protonic acid may be used as a solvent.

As the protonic acid, there may be exemplified organic acids (e.g.,organic carboxylic acids such as formic acid, acetic acid, propionicacid; hydroxycarboxylic acids such as oxalic acid, citric acid, tartaricacid; alkylsulfonic acids such as methanesulfonic acid, ethanesulfonicacid; arylsulfonic acids such as benzenesulfonic acid, p-toluenesulfonicacid), and inorganic acids (e.g., hydrochloric acid, sulfuric acid,nitric acid, phosphoric acid).

The oxidation process using the oxidation catalyst or the oxidationcatalytic system is characterized in that the oxidation reactionsmoothly proceeds even under comparatively mild or moderate conditions.The reaction temperature may be suitably selected according to thespecies of the catalytic system. The temperature is, for instance, about0 to 300° C., preferably about 30 to 250° C., more preferably about 50to 200° C., and practically about 70 to 150° C. In the production of anadamantanepolyol, the reaction at a temperature of about 40 to 150° C.,in particular about 60 to 120° C. (e.g., about 70 to 110° C.) tend toprovide an adamantanepolyol within a short period of time.

The reaction may be carried out under ambient pressure (atmosphericpressure) or under pressure (under a load). When the reaction isconducted under pressure, the pressure is, usually, about 1 to 100 atm(e.g., about 1.5 to 80 atm), preferably about 2 to 70 atm, and morepreferably about 5 to 50 atm. The reaction time may be suitably chosenwithin a range of about 30 minutes to 48 hours, preferably about 1 to 36hours, and more preferably about 2 to 24 hours, according to thereaction temperature and pressure.

[A carboxyl group-containing adamantane derivative]

As a process for introducing a carboxyl group to an adamantane, variousprocesses are available. In order to produce a carboxyl groupefficiently, it is advantageous to employ a carboxylation process whichcomprises, as in the oxidation reaction, contacting an adamantane withcarbon monoxide and oxygen in the presence of a catalyst comprising theimide compound (2) or a catalytic system comprising the imide compound(2) and a co-catalyst.

Carbon monoxide or oxygen used in the carboxylation reaction may be pureor diluted with an inert gas. Air may be used as an oxygen source.

In the carboxylation reaction, the amount of the imide compound shown bythe formula (2), the amount of the co-catalyst, and the ratio of theimide compound (2) to the co-catalyst may be selected within each rangementioned in the paragraphs of the oxidation reaction.

The amount of the carbon monoxide is selected within the range of 1 moleor more (e.g., about 1 to 1000 mole), preferably excess mole, forexample 1.5 to 100 mole, (e.g., about 2 to 50 mole), and more preferablyabout 2 to 30 mole (e.g., about 5 to 25 mole) relative to 1 mole of asubstrate.

The amount of oxygen is selected within the range of 0.5 mole or more(e.g., about 0.5to 100 mole), preferably about 0.5 to 30 mole, and morepreferably about 0.5 to 25 mole relative to 1 mole of a substrate.

The ratio of the carbon monoxide (CO) to oxygen (O₂) may be selectedwithin the broad range as far as being within the above mentioned range,for example CO/O₂=about 1/99 to 99.99/0.01 (mole %). It is advantageousto employ carbon monoxide in an amount larger than that of oxygen. Theratio of CO to O₂ may be selected within the range of about CO/O₂=1/99to 99/1 (mole %) [e.g., about 10/90 to 99/1 (mole %)], and is preferablyabout 30/70 to 98/2 (mole %), more preferably about 50/50 to 95/5 (mole%), and practically about 60/40 to 90/10 (mole %).

The volume ratio of carbon monoxide to oxygen in the supply line may beselected within the range of, for example, CO/O₂=about 1/99 to99.99/0.01 (volume %), and is, for example, usually about 1/99 to 99/1(volume %), preferably about 30/70 to 98/2 (volume %), more preferablyabout 50/50 to 95/5 (volume %), and practically about 60/40 to 90/10(volume %).

The carboxylation reaction may be carried out in an organic solventinert to the reaction. As the organic solvent, the organic solventexemplified for the oxidation reaction, such as an organic acid (e.g.,carboxylic acids such as acetic acid), a nitrile (e.g., acetonitrile)and a hydrocarbon halide (e.g., dichloroethane), may be used.

The carboxylation reaction using the imide compound (2) proceed smoothlyeven under comparatively mild or moderate conditions. The reactiontemperature may be selected within the range of, for example, about 0 to200° C., preferably about 10 to 150° C. (e.g., about 10 to 120° C.), andmore preferably about 10 to 100° C. (e.g., about 10 to 80° C.) accordingto the species of the imide compound or the substrate. The reaction maybe carried out under ambient pressure (atmospheric pressure) or underpressure (under a load).

[A hydroxymethyl group-containing adamantane]

A hydroxymethyl group-containing adamantane derivative may be producedby reducing the carboxyl group-containing adamantane derivative by aconventional process such as a catalytic hydrogenation using hydrogen orby a process using a hydrogenation reducing agent. A hydrogenationreducing agent includes, for example, sodium boron hydride-Lewis acid,aluminium hydride, lithium aluminium hydride, lithium trialkoxyaluminiumhydride, and diborane.

[An adamantane having a nitro group or an amino group]

Introduction of a nitro group to an adamantane or an adamantane having asubstituent may be carried out by a conventional process, for example, aprocess using a nitrating agent (e.g., a mixed acid of sulfuric acid andnitric acid, nitric acid, nitric acid and an organic acid (e.g.,carboxylic acids such as acetic acid), a nitrate and sulfuric acid anddinitrogen pentaoxide). A preferred nitration process includes, forexample, a nitration process which comprises contacting an adamantanewith a nitrogen oxide in the presence or absent of the imide compoundshown by the formula (2). The nitration reaction is advantageouslycarried out in the presence of a catalytic system (a catalytic systemcomprising the imide compound shown by the formula (2) and theco-catalyst) similar to that used in the above-mentioned oxidationreaction.

The nitrogen oxide-may be respresented by the formula N_(x)O_(y)(whereinx denotes an integer of 1 or 2 and y denotes an integer of 1 to 6).

In the compound shown by the above formula, when x is 1, y is usually aninteger of 1 to 3; and when x is 2, y is usually an integer of 1 to 6.

Examples of such nitrogen oxide are N₂O, NO, N₂O₃, NO₂, N₂O₄, N₂O₅, NO₃and N₂O₆. These nitrogen oxides may be used independently or incombination.

The preferred nitrogen oxide includes (i) a nitrogen oxide (particularlyN₂O₃) generated by the reaction of at least one nitrogen oxide selectedfrom dinitrogen oxide (N₂O) and nitrogen monoxide (NO) with oxygen, or anitrogen oxide containing N₂O₃ as a main component and (ii) a nitrogendioxide (NO₂) or a nitrogen oxide containing NO₂ as a main component.

Nitrogen oxide N₂O₃ may be easily obtained by a reaction of N₂O and/orNO with oxygen. To be more concrete, it may be prepared by introducingnitrogen monoxide and oxygen to a reactor to produce a blue liquid N₂O₃.Therefore, the nitration reaction may be carried out by introducing N₂Oand/or NO and oxygen to a reaction system without previously producingN₂O₃ in advance.

Incidentally, oxygen may be pure or distilled with an inert gas (e.g.,carbon dioxide, nitrogen, helium and argon). Air may be used as anoxygen source.

In other embodiment, among nitrogen oxides, when nitrogen dioxide (NO₂)is used, a nitration reaction smoothly proceeds even in the absent ofoxygen. Therefore, a reaction system using NO₂ does not necessarilyrequire oxygen. NO₂ may be used with oxygen.

The amount of the imide compound shown by the formula (2) may beselected within the range similar to that of the oxidation of anadamantane with oxygen.

The amount of the nitrogen oxide may be selected, according to theamount of nitro group to be introduced, within the range of, forexample, about 1 to 50 mole, preferably about 1.5 to 30 mole and maypractically be about 2 to 25 mole relative to 1 mole of an adamantane.

The nitration reaction is usually carried out in an organic solventinert to the reaction. The organic solvent may be selected from thesolvents similar to those exemplified in the paragraphs of the oxidationreaction. As a solvent, an organic acid (e.g., carboxylic acids such asacetic acid), a nitrile (e.g., acetonitrile and benzonitrile) and ahydrocarbon halide (e.g., dichroloethane) are practically used.

When employing the catalyst comprising the imide compound (2), thenitration reaction smoothly proceeds even under comparatively mild andmoderate conditions. The reaction temperature is selected, according tothe species of the imide compound or a substrate, within the range of,for example, about 0 to 150° C., preferably about 25 to 125° C., andmore preferably about 30 to 100° C. The nitration reaction may becarried out under ambient pressure (atmospheric pressure) or underpressure (under a load).

An adamantane derivative having an amino group may be produced bysubjecting a nitro group-containing adamantane derivative to a reductionreaction. The reduction reaction may be carried out by a conventionalprocess such as a catalytic hydrogenation using hydrogen as a reducingagent and a reducing process using a hydrogenation reducing agent.

In the catalytic hydrogenation, for example, a metal simplesubstance(e.g., platinum, palladium, nickel, cobalt, iron and copper)and a compound comprising such metal element (e.g., platinum oxide,palladium black, palladium carbon and copper chromite) may be used as acatalyst. The amount of the catalyst is practically about 0.02 to 2 molerelative to 1 mole of an adamantane (substrate). In a catalytichydrogenation, the reaction temperature may be, for example, about −20to 100° C. (e.g., about 0 to 70° C.). A hydrogen pressure is practicallyabout 1 to 10 atm.

In the reducing process using a hydrogenation reducing agent, thehydrogenation reducing agent includes, for example, aluminium hydride,sodium boron hydride and diborane. The amount of the hydrogenationreducing agent is usually 1 mole or more (e.g., about 1 to 10 mole)relative to 1 mole of a substrate. In the reducing process using thehydrogenation reducing agent, the reaction temperature is practicallyabout 0 to 200° C. (e.g., about 0 to 170° C.).

The reduction reaction (the catalytic hydrogenation and the processusing the hydrogenation reducing agent) may be carried out in thepresence of a solvent (any solvent exemplified in the paragraphs of theoxidation reaction such as a carboxylic acid, an ether, an ester or anamide) inert to the reductive reaction.

A halogen-containing adamantane derivative may be produced by aconventional process, for example, by subjecting the hydroxylgroup-containing adamantane to a reaction with a halogenating agent(e.g., hydrogen chloride; phosphrus halogenide such as phosphoruspentachloride, phosphorus trichloride; and thionyl chloride) or withchlorine or bromine. An alkoxy group-containing adamantane derivativemay be obtained by reacting the hydroxyl group-containing adamantanewith alkyl halide. An alkoxycarbonyl group-containing adamantanederivative may be obtained by reacting a carboxyl group-containingadamantane (or a reactive derivative thereof) with an alcohol. An amidegroup-containing adamantane derivative (e.g., a carbamoylgroup-containing adamantane derivative which may have a substituent) maybe obtained by reacting a carboxyl group-containing adamantane (or areactive derivative thereof) with ammonia or an amine (a primary orsecondary amine).

An acyloxy group-containing adamantane derivative and an acylaminogroup-containing adamantane derivative may be obtained, for example, byallowing a hydroxyl group-containing adamantane and an aminogroup-containing adamantane derivative to react with an acylating agentrespectively. An alkoxycarbonyloxy group-containing adamantanederivative and an alkoxycarbonylamino group-containing adamantanederivative may be obtained, for example, by allowing a hydroxylgroup-containing adamantane derivative and an amino group-containingadamantane derivative to react with a halocarbonate respectively. Acarbamoyloxy group-containing adamantane derivative may be obtained, forexample, by allowing a hydroxyl group-containing adamantane derivativeto react with an isocyanate compound. An N-substituted aminogroup-containing adamantane derivative may be obtained, for example, byallowing the amino group-containing adamantane to react with ahydrocarbon halide (e.g., aliphatic hydrocarbon halide such asiodomethane, iodoethane, iodobutane, bromomethane, bromoethane,bromobutane, chloromethane, chloroethane). The reaction of the aminogroup-containing adamantane with the hydrocarbon halide may be carriedout in the presence of a dehalogenating agent comprising an organic orinorganic basic compound.

Incidentally, before, after or during the oxidation reaction, anitration reaction, a reductive reaction, or the esterificationreaction, a hydroxyl group, an carboxyl group, an amido group or anamino group may be protected by a protecting group by a conventionalprocess. The elimination of the protecting group may be carried out by aconventional process, for example, using an acid, an alkali, orion-exchange resin.

Among the polymerizable adamantane derivatives (1) and adamantanederivatives (1a), a compound having a basic group or an acidic group maybe in the form of a salt. A carboxyl group-containing adamantanederivative may form a salt by reacting with a basic compound (e.g., anorganic base such as an organic amine; and an inorganic base such asammonia and an alkali metal compound). An amino group-containingadamantane derivative may form a salt by reacting with an acid. The acidincludes, for example, an inorganic acid (e.g., hydrochloric acid,sulfuric acid and nitric acid) and an organic acid (e.g., an aliphaticcarboxylic acid such as acetic acid and propionic acid; an aromaticcarboxylic acid such as benzoic acid; an alkylsulfonic acid such asmethanesulfonic acid and ethanesulfonic acid; and an arylsulfonic acidsuch as benzenesulfonic acid and p-toluenesulfonic acid).

[A novel polymerizable adamantane derivative]

Among the compounds shown by the formula (1), the polymerizableadamantane derivative shown by the formula (3) is novel. Thepolymerizable adamantane derivative is useful as a raw material (apolymerizable monomer) of a functional polymer. In the formula (3), anatom or a group represented by R¹, R², R³ or R⁴ (e.g., a non-reactiveatom, a non-reactive group, a polymerizable unsaturated group, an aminogroup or a N-substituted amino group) includes an atom or a groupsimilar to that of the formula (1).

A typical compound of the polymerizable adamantane derivative includes,for example, a nitro group-containing polymerizable adamantanederivative such as 1-(meth)acryloyloxy-3-nitroadamantane,1,3-bis[(meth)acryloyloxy]-5-nitroadamantane; a carboxylgroup-containing polymerizable adamantane derivative such as1-carboxy-3-(meth)acryloyloxyadamantane,1-(meth)acryloyloxy-3-methoxycarbonyl adamantane,1-carboxy-3,5-bis[(meth)acryloyloxy]adamantane and1-(meth)acryloyloxy-3-(N,N-dimethylcarbamoyl)adamantane; a hydroxymethylgroup-containing adamantane derivative such as1-hydroxymethyl-3-(meth)acryloyloxyadamantane; an amino group or aN-substituted amino group-containing polymerizable adamantane derivativesuch as 1-acetylamino-3-(meth)acryloyloxyadamantane and1-(meth)acryloyloxy-3-methoxycarbonylaminoadamantane; and a polymerizaleadamantane derivative having not less than three polymerizableunsaturated groups such as 1,3,5-tris[(meth)acryloyloxy]adamantane. Asubstituent of these compounds may be protected by a protecting group.

A polymerizable adamantane derivative (3) may be obtained by a reactionsimilar to the above reaction (e.g., the oxidation reaction, thecarboxylation reaction, the nitration reaction, the esterificationreaction and the amidation reaction). In the production of thepolymerizable adamantane derivative (3), the esterification reactionand/or the amidation reaction may be carried out by a conventionalmanner, for example, in the presence of an acid catalyst or an alkalicatalyst, and advantageously in the presence of a catalyst comprisingthe compound containing a Group 3 element of the Periodic Table ofElements.

Incidentally, a reaction such as the oxidation reaction may be carriedout in any of a batch system, semi-batch system or continuous system.After completion of the reaction, a reaction product can be easilyisolated and purified according to a conventional technology, such asfiltration, condensation, distillation, extraction, crystallization,recrystallization, column chromatography, or other isolation means, or acombination of these technologies.

A preferred polymerizable adamantane derivative and a polymer thereofinclude an adamantane derivative in which a residual amount by weight ofa halogen is 70 ppm or less (e.g., about 0 to 60 ppm), preferably 50 ppmor less, more preferably 25 ppm or less (e.g., about 0 to 15 ppm) andparticularly 10 ppm or less (e.g., 5 ppm or less). In a most preferredplymerizable adamantane derivative is one in which a halogen componentis not detected substantially and the residual amount by weight of ahalogen is 1 ppm or less. The species of halogen is not particularlyrestricted, and it may be fluorine or iodine, and is practicallychlorine or bromine.

A polymer of the polymerizable adamantane derivative may be ahomopolymer or a copolymer with a copolymerizable monomer.

These polymerizable adamantane derivatives may be obtained by allowingthe adamantane derivative shown by the formula (1a) (e.g., a hydroxylgroup-containing adamantane derivative) to react with at least onepolymerizable compound (1b) (e.g., an organic carboxylic acid, anorganic carboxylic acid alkyl ester and an organic carboxylic acidalkenyl ester having α,β-ethylentically unsaturated double bond ortriple bond) selected from the group consisting of an alcohol, acarboxylic acid, an amine and a reactive derivative, containg no halogenatom thereof each having a polymerizable unsaturated bond in thepresence of the compound containing a Group 3 elements of the PeriodicTable of Elements.

Moreover, in order to reduce the residual amount of a halogen, it ispreferable that an adamantane derivative induced with no reactive group,among the adamantane derivatives shown by the formula (1a) is subjectedto at least one step selected from the following oxidation step (i), thecarboxylation step (ii) and the nitration step (iii) to produce acompound introduced with at least one reactive group selected from thegroup consisting of a hydroxyl group, a carboxyl group and a nitrogroup, and the resultant compound is subjected to the esterification oramidation reaction:

(i) an oxidation step with oxygen in the presence of a catalystcomprising the imide compound shown by the formula (2);

(ii) a carboxylation step with carbon monoxide and oxygen in thepresence of a catalyst comprising the imide compound shown by theformula (2); and

(iii) at least one of a nitration step among the following (iiia),(iiib) and (iiic)

(iiia) a nitration step by a nitrogen oxide in the presence of acatalyst comprising the imide compound shown by the formula (2);

(iiib) a nitration step by at least one of a nitrogen oxide among adinitrogen oxide and nitrogen monoxide with oxygen; and

(iiic) a nitration step by nitrogen dioxide.

The adamantane derivative to which no reactive group is introducedincludes an adamantane derivative of the formula (1a) wherein R^(1a),R^(2a), R^(3a) and R^(4a) are same or different from each other andrepresent a hydrogen atom, a non-reactive atom or a non-reactive group,and at least one member selected from R^(1a), R^(2a), R^(3a), and R^(4a)is a hydrogen atom.

Incidentally, at least one group selected from a hydroxymethyl group andan amino group may be produced by subjecting the reaction productobtained at the carboxylation step (ii) and/or the nitration step (iii)to a reduction step.

Such polymerizable adamantane derivative and polymer thereof (ahomopolymer or a copolymer) contain a considerable little residualamount of a halogen, and are preferable at the point of safetysanitation and environment sanitation, and may inhibit coloring.

INDUSTRIAL APPLICABYLITY

A polymerizable adamantane derivative obtained by a process of thepresent invention can be thermal polymerizable and photopolymerizable inthe presence or absent of a polymerization initiator (or aphotopolymerization initiator). A polymer of the polymerizableadamantane derivative is superior in optical characters, machinecharacters, thermal characters and electrical characters. Therefore, thepolymerizable adamantane derivative may be utilized for variouspurposes, for example, as a high-functional material (e.g., an opticalmaterial such as an optical fiber or covering agent thereof, an opticalelement, an optical lens, a hologram, an optical disk, and a contactlens, a coating agent for an organic glass, a conductive polymer, aphotographic photosensitive material and a fluorescent material), acoating agent (including a paint), adhesives and a reforming agent of apolymer.

In the present invention, while inhibiting a halogen component frommixing, an adamantane derivative having a polymerizable unsaturatedgroup can be obtained in high yield. A highly pure polymerizableadamantane derivative may be effectively obtained in high efficiency. Inparticular, while side reaction is inhibited, a polymerizableunsaturated group can be efficiently introduced to an adamantanederivative.

A polymerizable adamantane derivative of the present invention is usefulfor obtaining a functional polymer having superior characters.

The following example are intended to describe the present invention inmore detail, but should by no means be construed to limit the scope ofthe invention. Inorganic acid ion, such as halogen compound ions andnitric acid ion were analyzed by liquid chromatography for aniondetection.

EXAMPLES Preparation Example 1

To 25 mmol of acetic acid were added 10 mmol of adamantane, 1 mmol ofN-hydroxyphthalimide (NHPI) and a binary co-catalyst [0.03 mmol ofacetylacetonatovanadium V(AA)₃ and 0.02 mmol of actylacetonatomanganMn(AA)₃], and the resultant mixture was stirred in an oxygen atmosphereat a temperature of 75° C. for 6 hours. The products in the reactionmixture were analyzed by gas chromatography, and, as a result, theadamantane was converted into 1-adamantanol (yield: 37%).1,3-adamantanediol (yield: 35%). 1,3,5-adamantanetriol (yield: 5%),1,3,5,7-adamantane-tetranol (yield: 4%) with the adamantane conversionof 100%. The spectrum data of the 1,3,5,7-adamantanetetranol was asfollows:

¹H-NMR(CDCl₃)δ: 1.602, 4.893

¹³C-NMR(CDCl₃)δ: 52.3, 71.6

IR(cm⁻¹): 3306, 2947, 1455, 1332, 1210, 1046, 1004, 971, 559

Preparation Example 2

To 25 ml of acetic acid were added 10 mmol of adamantane,2 mmol of NHPIand 0.1 mmol of acetylacetonatovanadium V(AA)₃, and the resultantmixture was stirred in an oxygen atmosphere at a temperature of 85° C.for 10 hours. The analysis of the product in the reaction mixturerevealed that the adamantane was converted into 1-adamantanol (yield:8%), 1,3-adamantanediol (yield: 22%), 1,3,5-adamanetriol (yield: 33%)and 1,3,5,7-adamantanetetraol (yield: 20%) with the adamantaneconversion of 99%.

Preparation Example 3

To 25 ml of acetic acid were added 10 mmol of adamantane, 0.8 mmol ofNHPI and 0.6 mmol of acetylacetonatocobalt(II)Co(AA)₂ , and theresultant mixture was stirred in an oxygen atmosphere at a temperatureof 75° C. for 3 hours. The products in the reaction mixture wereanalyzed by gas chromatography, and, as a result, adamantane wasconverted into 1-adamantanol (yield: 48%) and 1,3-adamantanediol(yield:13%) with the adamantane conversion of 65%.

Comparative Example 1

To 2 ml of dioxane were added 0.168 g (1.00 mmol) of adamantanediol and0.222 g (2.20 mmol) of triethylamine at a temperature of 50° C. To theresultant mixture was added dropwise in dioxane (2 ml) a solution ofwith 0.2 g (2.20 mmol) of acrylic acid chloride at a temperature of 50°C. for 1 hour, and then, the resultant mixture was stirred at atemperature of 50° C. for 1 hour. The product in the reaction mixturewas analyzed by gas chromatography, and the analysis revealed theformation of 0.204 g of adamantanediacrylate (yield: 74%).

Comparative Example 2

0.168 g (1.00 mmol) of adamantanediol and 0.222 g (2.20 mmol) oftriethylamine were dissolved in 2 ml of dioxane at a temperature of 50°C. To the resultant mixture was added dropwise a solution of 0.230 g(2.20 mmol) methacrylic acid chloride in dioxane (2 ml) at a temperatureof 50° C. for 1 hour, and then, the resultant mixture was stirred at atemperature of 50° C. for 1 hour. The analysis by gas chromatographyrevealed that the product in the reaction mixture was 0.237 g ofadamantane-dimethacrylate (yield: 78%).

Comparative Example 3

To 2 ml of dioxane were added 0.168 g (1.00 mmol) of adamantanediol,0.019 g (0.10 mmol) of p-toluenesulfonic acid and 0.159 g (2.20 mmol) ofacrylic acid, and the resultant mixture was stirred at a temperature of50° C. for 8 hours. The analysis by gas chromatography revealed theformation of 0.224 g of adamantane-diacrylate (yield: 81%).

Comparative Example 4

The reaction was conducted in the same manner as in comparative example1 except that 1 mmol of adamanetanol, 1.20 mmol of trietylamine, 1.2mmol of acrylic acid chloride and 2 ml of dioxane were used, and 0.167 gof adamantanemonoacrylate (yield: 81%) was formed.

Comparative Example 5

The reaction was conducted in accordance with the method of The JapanesePatent Publication No. 61980/1995 (JP-B-7-61980) to obtain an adamantanemonoaclylate, namely, 15 mole of anhydrousbromine and 1.6 mole ofadamantane were reacted at the reflux temperature of bromine for 7hours, surplus bromine was distilled off under reduced pressure, andafter the addition of 200 ml of carbon tetrachloride (IV), the residualbromine was resolved with sodium sulfite. A white powderly1-bromoadamantane was provided by removing organic layer, andrecrystallizing the obtained crude products from methanol.

The obtained 1 mol of 1-bromoadamantane, 400 ml of 0.67 N-hydrochloricacid and 450 ml of dimethylformamide and the resultant were stirred atthe reflux temperature for 1 hour. Then, the solid product was filtratedand recrystallized from n-hexane to produce a white needle1-hydrxyadamantane.

To 200 ml of toluene were added 0.1 mole of 1-hydroxyadamantane, 0.2mole of acrylic acid, 0.06 mole of p-toluene sulfinic acid and 0.2 moleof p-methoxyphenol, and the resultant mixture was stirred at the refluxtemperature to esterify reacted while collecting the provided water tothe point where the amount of produced water reached the theoreticalamount. The reaction product was neutralized by 10 parts by weight ofsodium hydroxide solution, and the precipitate produced was separated byfiltration, and the toluene was distilled off under reduced pressure.The resultant crude product was recrystalized from n-hexane to obtain anadamantane monoacrylate.

Comparative Example 6

To 324 ml of 70% sulfuric acid was added 0.33 mole of the1-hydroxyadamantane obtained in Comparative Example 5, and the resultantmixture was stirred at the temperature of 95° C. for 4 hours. Thereaction product was poured into ice water extracted with ethanol. Thewater phase was neutralized by sodium hydroxide and extracted withn-butanol, then the solvent was distilled off from the extract underreduced pressure. The crude product was recrystallized from n-hexane toobtain a powderly 1,3-dihydroxyadamantane.

The esterification was conducted in the same manner as in ComparativeExample 5 except that the obtained 1,3-dihydroxadamantane was usedinstead of using the 1-hydroxyadamantane of Comparative Example 5 toobtain an adamantane diacrylate.

Example 1

To 2 ml of dioxane were added 0.168 g (1.00 mmol) of adamantanediol,0.040 g (0.010 mmol) of samarium iodide (SmI₂) and 0.216 g (2.20 mmol)of vinyl acrylate, and the resultant mixture was stirred at atemperature of 50° C. for 6 hours. The analysis by gas chromatographyrevealed the formation of 0.273 g of an adamantanediacrylate (yield:99%, white solid) in the reaction mixture.

Example 2

The reaction was conducted in the same manner as in Example 1 exceptthat 2.20 mmol of isopropenyl was used instead of the vinyl acrylate andthat the reaction time was 4 hours. As a result, 0.273 g (yield: 97%,white solid) of an adamantanediacrylate was formed in the reactionmixture.

Example 3

To 2 ml of dioxane were added 0.168 g (1.00 mmol) of adamantanediol,0.040 g (0.10 mmol) of samarium iodide (SmI₂) and 0.247 g (2.20 mmol) ofvinyl methacrylate, and the resultant mixture was stirred at atemperature of 50° C. for 6 hours. The analysis of the product revealedthat the formation of 0.292 g of an adamantanedimethachrilate (yield:96%, white solid) in the reaction mixture.

Example 4

The reaction was conducted in the same manner as in Example 3 exceptthat 2.20 mmol of isopropenyl methacrylate was used instead of the vinylmethacrylate and that the reaction time was shortened to 4 hours. In thereaction mixture 0.301 g of adamantanediacrylate (yield: 98%) wasformed.

Example 5

To 2 ml of dioxane were added 0.168 g (1.00 mmol) of adamantanediol,0.045 g (0.10 mmol) of di(η⁵-pentametylcyclopentadienyl)samarium [CP^(*) ₂ Sm(THF)₂ ]and 0.216 g (2.20 mmol) of vinyl acrylate, and theresultant mixture was stirred at a temperature of 50° C. for 6 hours.The analysis by gas chromatography revealed the formation of 0.271 g(yield: 98%) of an adamantanediacrylate in the reaction mixture.

Example 6

To 2 ml of dioxane were added 0.168 g (1.00 mol) of adamantanediol,0.045 g (0.10 mmol) of C^(*) ₂Sm(THF)₂ and 0.247 g (2.20 mmol) of vinylmethacrylate, and the resultant mixture was stirred at a temperature of50° C. for 6 hours. The analysis by gas chromatography revealed theformation of 0.295 g of adamantanedimethacrylate (yield: 97%) in thereaction mixture.

Example 7

To 2 ml of dioxane were added 0.168 g (1.00 mmol) of adamantanediol,0.045 g (0.10 mmol) of Cp^(*) ₂Sm (THF)₂, 0.247 g (2.20 mmol) of vinylacrylate and 0.023 g (0.20 mmol) of cyclohexaneoxime, and the resultantmixture was stirred at a temperature of 50° C. for 4 hours. The analysisby gas chromatography revealed the formation of 0.271 g ofadamantanediacrylate (yield: 98%) in the reaction mixture.

Examples 8 and 9

The reaction was conducted in the same manner as in Example 1 exceptthat 0.1 mmol of samariumtriflate (III)(Example 8), 0.1 mmol ofscandiumtriflate (Example 9) were used instead of the samarium iodide ofExample 1. The results were the same as those of Example 1 (0.265 g ofadamantanediacrylate (yield: 96%).

Example 10

The reaction was conducted in the same manner as in Example 1 exceptthat 1 mmol of adamantanol, 0.1 mmol of samarium iodide, 4.5 mmol ofvinyl acrylate and dioxane (2 ml) were used, and resulted in theformation of 0.204 g of adamantanemonoacrylate (yield: 99%, colorlessliquid).

Example 11

The reaction was conducted in the same manner as in Example 1 exceptthat 1 mmol of adamantanetetraol, 0.1 mmol of samarium iodide, 4.5 mmolof vinyl acrylate and dioxane (2 ml) were used, and resulted in theformation of 0.395 g of adamantanetetracrylate (yield: 95%, whitesolid).

And then, the reaction mixtures of Comparative Examples 1, 2 and 4,Examples 1˜8 and 10 were distilled under reduced pressure to remove asolvent and a reaction agent, and the yield of the object compound wasmeasured. And then, the products by distillation under reduced pressurewere refined by being subjected to column separation (column: wako-gelC-300, elution solvent: n-hexane/ethyl acetate=8/2 (V/V)).

The refined products by column separation, those of Comparative Examples1, 2 and 4 containing chlorine, were recrystallized twice and thecontent of the chlorine was reduced to 10 ppm or less. Further, thecontent of the chlorine in the refined products by column separation was700 ppm in Comparative Example 1, 850 ppm in Comparative Example 2, 930ppm in Comparative Example 4. The amount of halogen contained in eachproduct and refined product by column separation obtained in Examples1-10 was not more that 10 ppm, thus, no recrystalliation was occurred.

The yields (isolation yield) of the object compounds obtained by thereaction and refining are shown in Table 1.

TABLE 1 Yield (%) After the In the distillation After the After thereaction in reduced separation recrystalli- mixture pressure by thecolumn zation Com. Ex. 1 74 68 64 49 Com. Ex. 2 78 72 69 58 Com. Ex. 481 74 69 61 Ex. 1 97 94 91 N.R. Ex. 2 99 96 92 N.R. Ex. 3 96 94 90 N.R.Ex. 4 99 96 93 N.R. Ex. 5 98 95 91 N.R. Ex. 6 97 95 92 N.R. Ex. 7 98 9390 N.R. Ex. 8 96 92 88 N.R. Ex. 10 99 98 95 N.R. N.R.: Recrystallizationis not required.

[Physical properties of polymer]

To (i) the adamantanediacrylate (Example 1, Comparative Example 6), (ii)the adamantanemonoacrylate (Example 10, Comparative Example 5), (iii) amixture of the 50% by weight adamantaemonoacrylate (Example 10) and 50%by weight methyl methacrylate (AMA-MMA39), (iv) a mixture of the 50% byweight adamantane monoacrylate (Example 10) and 50% by weight diethyleneglycol bis allylcarbonate (CR39) (AMA-CR39) and (v) methyl methacrylate(MMA) were added 0.1 part by weight of photo-polymerization initiator(benzophenone). The mixture was applied to glass plate andphoto-polymerized by irradiation of ultraviolet rays.

Physical properties of the obtained polymer were measured and theresults are shown in Table 2.

The properties of the polymer in the Table were measured based on thefollowing conditions,

Refractive index: measured with Abbe's refractometer NAR-L (light sourceNa-d, 587.6 nm), manufactured by ATAGO Co., Ltd.

Light-transmisson: ASTM-D1003

Double refraction: measured in accordance with the method of Senarmonwith He-Ne laser

Pencil hardness: measured with pencil hardness tester, manufactured byKANEHISA Co., Ltd.

Thermal deformation point: measured with oil-carried thermal deformationmeter, manufactured by YASUDASEIKI Co., Ltd.

Water absorption (%): soaked in boiling water at 100° C. for two hoursand measured

Content of the halogen (bromine): the standard solution containing 5 ppmof bromine was prepared by thinning the standard solution for atomicabsorption spectrometry with pure water in order. Drew the calibrationcurve with the prepared standard solution, and measured with atomicabsorption spectrometer (AA-6700, manufactured by SHIMAZU Co., Ltd.).

Coefficient of polycondensation: measured the mass of the polymer beforeand after polymerization with a measuring cylinder in the water at 25°C.

Coefficient of polycondensation shows the coefficient of condensation,as a result of polymerization from monomer to polymer.

TABLE 2 AMA- AMA- Com. Com. Ex. 10 Ex. 1 MMA CR39 Ex. 5 Ex. 6 Specificgravity  1.017  1.015  1.072  1.055  1.018  1.014 (g/cm³) Refractive 1.535  1.537  1.52  1.52  1.50  1.51 index (nD₂O) Dispersing  53.0 56.3  56.8  56.1  51.1  55.8 index (%) Transmittance  92  92  92  92 90  91 (%) Birefringence  50>  50>  50>  50>  50<  50< (nm) Hardness of 4 H  4 H  3 H  3 H  4 H  4 H pencil Water  0.13  0.08  0.14  0.12  0.13 0.08 absorption (%) Polymerization  7.7  8.1  10.5  9.0  7.7  8.1shrinking index (%) Temperature of 160 200< 136 124 160 200< thermalDeformation (° C.) Glass transition 178 200< 155 140 178 200<Temperature (° C.) Color number  5  3  10  8  66  52 Content of Br  1> 1>  1>  1> 127 105 (ppm)

Preparation Example 4

A flask with side arms (50 ml) was immersed in ice water, and thepressure was reduced. Nitrogen monoxide was introduced into the flaskfrom a gas pack (1L) and oxygen was introduced into the flask from a gaspack (1L) at the same time. The flask was filled with a reddish browngas, and a blue liquid or solution containing mainly N₂O₃ was formed asthe brownish red gas settled. The said introduction of nitrogen monoxideand oxygen was alternately repeated to produce about 1.5 L of a blueliquid or solution, and it was frozen with liquid nitrogen.

To 5 ml of acetate were added 1.8 g (N₂O₃ conversion is 0.024 mol) of afrozen blue solution, 1 mmol of adamantane and 0.05 mmol of NHPI, andthe resultant mixture was reacted with stirring at a temperature of 100°C. for 10 hours to form a 1-ntroadamantane and a 1,3-dinitroadamantane.

To 25 ml of acetic acid were added 10 mmol of 1-nitroadamantane, 1 mmolof NHPI and 0.05 mmol of V(AA)₃, and the resultant mixture was stirredin an oxygen atmosphere at a temperature of 75° C. for 8 hours. Theanalysis by gas chromatography revealed the formation of1-nitro-3-adamantanol (yield: 48%) a 1-nitro-3,5-adamantanediol(yield:19%) and a 1-nitro-3,5,7-adamantanetriol (yield:2%), convertedfrom 1-nitroadamantane at a conversion rate of 76%. These products wereanalyzed by mass spectrometric analysis.

(1) 1-nitro-3-adamantanol

Light yellow solid

Mass spectrum data (fragment)

[M]⁺: 181, [M]⁻: 163 (—OH₂), [M]⁻⁻: 117(—NO₂)

(2) 1-nitro-3,5-adamantanediol

Light yellow solid

Mass spectrum data (fragment)

[M]⁺: 197, [M]⁻: 179 (—OH₂), [M]⁻⁻: 133(—NO₂)

Preparation Example 5

To 25 ml of acetic acid were added 10 mmol of adamantane, 1 mmol of NHPIand 0.005 mmol of Co (AA)₂. A gas pack containing a mixed gas (2 L ofcarbon monoxide and 0.5 L of oxygen) was connected to a reactor, and theobtain mixture was stirred at a temperature of 60° C. for 6 hours to1-carboxyadamantane (white solid) and a 1,3-dicarboxyadamantane.

To 25 ml of acetic acid were added 10 mmol of 1-carboxyadamantane, 1mmol of NHPI and 0.05 mmol of V (AA)₃, and the resultant mixture wasstirred in an oxygen atmosphere at a temperature of 75° C. for 5 hours.And, as a result, the 1-carboxyadamantane was converted into a1-carboxy-3-adamantanol (yield: 56%, white solid), a1-carboxy-3,5-adamantanediol (yield:28%, light yellow solid), a1-carboxy-4-adamantanone (yield: 4%) with a conversion of 99%.

Preparation Example 6

10 mmol of the 1-carboxy-3-adamantanol produced by the method ofPreparation Example 5 under a nitrogen atmosphere was dissolved in 10 mlof DMF, and 15 mmol of thionyl chloride was dropped into the solutionfor 30 minutes. The temperature was elevated so that the solution startsits reflux at the end of dropping. After two hours of reflux, thereactant mixture was cooled, added 20 mmol of triethylamine, thetemperature of the mixture was maintained at 10° C. or below, and 11mmol of methanol was added dropwise for 30 minutes and stirred for 2hours. And, at the result, the 1-carboxy-3-adamantanol was convertedinto a 1-methoxycarbonyl-3-adamantanol (yield: 95%) with a conversion of99%.

White solid

Mass spectrum data [M]⁺: 210

IR (cm⁻¹): 3350, 1730, 1130

Preparation Example 7

To 25 ml of acetic acid were added 10 mmol of adamantane, 1 mmol of NHPIand 0.05 mmol of acethylacetonatocobalt(II) (Co(AA)₂), and the resultantmixture was stirred in an oxygen atmosphere at a temperature of 75° C.for 6 hours. The adamantane was converted into a 1-acethyloxyadamantane(white solid) and a 1,3-diacethyloxyadamantane (white solid).

To 25 ml of acetic acid were added 10 mmol of said1-acethyloxyadamantane, 1 mmol of NHPI and 0.05 mmol of V (AA)₃, and theresultant mixture was stirred in an oxygen atmosphere at a temperatureof 75° C. for 8 hours. And, as a result, the 1-acethyloxyadamane wasconverted into a 1-acethyloxy-3-adamantanol (yield:37%), a1-acethyloxy-3,5-adamatanediol (yield:25%) and a1-acethyloxy-3,5,7-adamantanetriol (yield:11%) with a conversion of 89%.

(1) 1-acethyloxy-3-adamantanol

White solid

Mass spectrum data (fragment)

[M]⁺: 210, [M]⁻: 151 (-OA_(C)), [M]⁻⁻: 133 (—OH₂)

(2) 1-acethyloxy-3,5-adamantanediol

White solid

Mass spectrum data (fragment)

[M]⁺: 226, [M]⁻: 167 (—OA_(C)), [M]⁻⁻: 149 (—OH₂)

Preparation Example 8

15 mmol of aluminiumlitium hydroxide was suspended in 15 ml oftetrahydrofuran (THF) in a nitrogen atmosphere. To the solution wasslowly added 10 mmol of the 1-carboxy-3-adamantanol obtained inPreparation Example 5 while the temperature of the solution wasmaintained at less than 10° C. or below by ice water bath. After thetemperature of the mixture was raised to room temperatures, the mixturewas refluxed for 16 hours. And, as the result, the1-carboxy-3-adamantanol was converted into a1-hydroxymethyl-3-adamantanol (yield: 95%) with a conversion of 99%.

White solid

Mass spectrum data [M]⁺: 182

IR (cm⁻¹): 3370, 1380, 1120

Preparation Example 9

An autocrave was charged with 10 ml of methanol were added 10 mmol ofthe 1-nitro-3-adamantanol obtained by the method of Preparation Example4, 5% Pd-C (10 mol % as Pd, relative to a substrate) and 1 ml ofhydrochloric acid, and the mixture was stirred in a hydrogen atmosphereat a temperature of 80° C. for 2 hours. And, as a result, the1-nitro-3-adamantanol was converted into a 1-amino-3-adamantanol(yield:95%) with a conversion of 99%.

Light yellow solid

Mass spectrum data [M]⁺: 167

IR (cm⁻¹): 3370, 3340, 1620, 1360

11 mmol of acetyl chloride and 12 mmol of triethylamine were dissolvedin 2 ml of THF in a nitrogen atmosphere, and to the reactant solutionwas dropped 10 mmol of DMF (10 ml) solution with said1-amino-3-adamantanol at a temperature of 40° C. for 30 minutes. Then,the reactant mixture was stirred at a temperature of 40° C. for 3 hours.And, as a result, the 1-amino-3-adamantanol was converted into a1-acetylamino-3-adamantanol (yield: 95%) with a conversion of 99%.

Light yellow solid

Mass spectrum data [M]⁺: 209

IR (cm⁻¹): 3350, 1670, 690

Preparation Example 10

To 25 ml of acetic acid were added 10 mmol of 1,3-adamantanediol, 1 mmolof NHPI and 0.05 mmol of acetylacetonatovanadium (III) (V(AA)₃), and theresultant mixture was stirred in an oxygen atmosphere at a temperatureof 75° C. for 6 hours. And, as a result, the 1,3-adamantanediol wasconverted into a 1,3,5-adamantanetriol (yield: 80%) with a conversion of99%.

White solid

Mass spectrum data [M]⁺: 184

IR (cm⁻¹): 3320, 1320, 1170

Preparation Example 11

A flask with side arms (50 ml) was immersed in ice water, and thepressure was reduced. Oxygen was introduced into the flask from the gaspack (1L) while nitrogen monoxide was introduced into the flask from thegas pack (1L), flask was filled with a brownish red gas and a bluesolution whose principal ingredient was N₂O₃ was produced as thebrownish red gas was precipitated. The said introductions of nitrogenmonoxide and oxygen were repeated so as to produce about 1.5 L of bluesolution, and the blue solution was frozen with liquid nitrogen.

To 5 ml of acetic acid were added 1.8 g (0.024 mol, in terms of N₂O₃) ofthe frozen blue solution, 1 mmol of 1, 3-adamantanediol and 0.05 mmol ofNHPI, and the resultant mixture was reacted with stirring at atemperature of 100° C. for 10 hours, and, as a result, the1,3-adamantanediol was converted into a 1-nitro-3,5-adamantanediol(yield:80%) with a conversion of 99%.

Light yellow solid

Mass spectrum data [M]⁺: 213

IR (cm⁻¹): 3320, 1320, 1170

Preparation Example 12

To 25 ml of acetic acid were added 10 mmol of 1,3-adamantanediol, 1 mmolof NHPI and 0.005 mmol of Co (AA)₂, a gas pack containing a mixed gas (2lit. of carbon monoxide and 0.5 lit. of oxygen; pressure:5 kg/cm²) wasconnected with the reactor, and the resultant mixture was stirred at atemperature of 60° C. for 6 hours. And, as a result, the1,3-adamantanediol was converted into a 1-carboxy-3,5-adamantanediol(yield: 80%) with a conversion of 99%.

White solid

Mass spectrum data [M]⁺: 212

IR (cm⁻¹): 3320, 1320, 1170

Example 12

The reaction was conducted in the same manner as in Example 2 exceptthat 1.00 mmol of the 1-nitro-3-adamantanol obtained by the method ofPreparation Example 4 and 1.10 mmol of isopropenil acrylate were usedinstead of the adamantanediol, and, as a result, a1-acryloiloxy-3-nitroadamantane was obtained with a yield of 99%.

Light yellow solid

Mass spectrum data [M]⁺: 251

IR (cm⁻¹): 1730, 1560, 1450, 1120

Example 13

The reaction was conducted in the same manner as in Example 4 exceptthat 1.00 mmol of the 1-nitro-3-adamantanol obtained by the method ofPreparation Example 4 and 1.10 mmol of isopropenil methacrylate wereused instead of the adamantanediol, and, as a result, a1-methacryloiloxy-3-nitroadamantane was obtained with a yield of 99%.

Light yellow solid

Mass spectrum data [M]⁺: 265

IR (cm⁻¹): 1720, 1550,1460, 1140

Example 14

The reaction was conducted in the same manner as in Example 2 exceptthat 1.00 mmol of the 1-carboxy-3-adamantanol obtained by the method ofPreparation Example 5 and 1.10 mmol of isopropenil acrylate were usedinstead of the adamantanediol, and, as a result, a1-acryloiloxy-3-carboxyadamantane was obtained with a yield of 99%.

White solid

Mass spectrum data [M]⁺: 250

IR (cm⁻¹): 3030, 1670, 1620, 1430

Example 15

The reaction was conducted in the same manner as in Example 4 exceptthat 1.00 mmol of the 1-carboxy-3-adamantanol obtained by the method ofPreparation Example 5 and 1.10 mmol of isopropenil methacrylate wereused instead of the adamantanediol, and, as a result, a1-carboxy-3-methacryloiloxyadamantane was obtained with a yield of 99%.

White solid

Mass spectrum data [M]⁺: 264

IR (cm⁻¹): 3020, 1670, 1630, 1450

Example 16

The reaction was conducted in the same manner as in Example 2 exceptthat 1.00 mmol of the 1-methoxycarbonyl-3-adamantanol obtained by themethod of Preparation Example 6 and 1.10 mmol of isopropenil acrylatewere used instead of the adamantanediol, and, as a result, a1-acryloyloxy-3-methoxycarbonyladamantane was obtained with a yield of99%.

Colorless viscid liquid

Mass spectrum data [M]⁺: 264

IR (cm⁻¹): 1620, 1440, 1240, 1030

Example 17

The reaction was conducted in the same manner as in Example 4 exceptthat 1.00 mmol of the 1-methoxycarbonyl-3-adamantanol obtained by themethod of Preparation Example 6 and 1.10 mmol of isopropenylmethacrylate were used instead of the adamantanediol, and, as a result,a 1-methacryloyloxy-3-methoxycarbonyladamantane was obtained with ayield of 99%.

Colorless viscid liquid

Mass spectrum data [M]⁺: 278

IR (cm⁻¹): 1620, 1460, 1240, 1010

Example 18

The reaction was conducted in the same manner as in Example 2 exceptthat 1. 10 mmol of isopropenyl acrylate, and, as a result, a1-acryloyloxy-3-adamantanol was obtained with a yield of 90%.

White solid

Mass spectrum data [M]⁺: 222

IR (cm⁻¹): 3320, 1620, 1440, 1240

Example 19

The reaction was conducted in the same manner as in Example 4 exceptthat 1.10 mmol of isopropenyl methacrylate, and, as a result, a1-methacryloyloxy-3-adamantanol was obtained with a yield of 90%.

White solid

Mass spectrum data [M]⁺: 236

IR (cm⁻¹): 3310, 1620, 1450, 1220

Example 20

The reaction was conducted in the same manner as in Example 2 exceptthat 1.00 mmol of the 1-acetyloxy-3-adamantanol obtained by the methodof Preparation Example 7 and 1.10 mmol of isopropenyl acrylate were usedinstead of the adamantanediol, and, as a result, a1-acetyloxy-3-acryloyloxyadamantane was obtained with a yield of 99%.

White solid

Mass spectrum data [M]⁺: 264

IR (cm⁻¹): 1660, 1450, 1240, 1010

Example 21

The reaction was conducted in the same manner as in Example 4 exceptthat 1.00 mmol of the 1-acetyloxy-3-adamantanol obtained by the methodof Preparation Example 7 and 1.10 mmol of isopropenyl methacrylate wereused instead of the adamantanediol, and, as a result, a1-acetyloxy-3-methacryloyloxyadamantane was obtained with a yield of99%.

White liquid

Mass spectrum data [M]⁺: 278

IR (cm⁻¹): 1660, 1470, 1240, 1030

Example 22

The reaction was conducted in the same manner as in Example 2 exceptthat 1.00 mmol of the 1-hydroxymethyl-3-adamantanol obtained by themethod of Preparation Example 8 and 1.10 mmol of isopropenyl acrylatewere used instead of the adamantanediol, and, as a result, (1)1-acryloiloxy-3-hydroxymethladamantane and (2)1-acryloyloxymethyl-3-adamantanol were obtained.

(1) 1-acryloyloxy-3-hydroxymethyladamantane

White solid

Mass spectrum data [M]⁺: 236

IR (cm⁻¹): 3330, 1490, 1440, 720

(2) 1-acryloyloxymethyl-3-adamantanol

White solid

Mass spectrum data [M]⁺: 236, [M]⁻: 218, [M]⁻⁻: 191,

[M]⁻⁻⁻: 147, [M]⁻⁻⁻⁻: 133

Example 23

The reaction was conducted in the same manner as in Example 4 exceptthat 1.00 mmol of the 1-hydroxymethyl-3-adamantanol obtained by themethod of Preparation Example 8 and 1.10 mmol of isopropenyl 4methacrylate were used instead of the adamantanediol, and, as a result,a 1-hydroxymethyl-3-meyhacryloyloxyadamantane was obtained with a yieldof 90%.

White solid

Mass spectrum data [M]⁺: 250

IR (cm⁻¹): 3320, 1500, 1420, 750

Example 24

The reaction was conducted in the same manner as in Example 2 exceptthat 1.00 mmol of the 1-acetylamino-3-adamantanol obtained by the methodof Preparation Example 9 and 1.10 mmol of isopropenyl acrylate were usedinstead of the adamantanediol, and, as a result, a1-acetylamino-3-acryloyloxyadamantane was obtained with a yield of 99%.

Light yellow solid

Mass spectrum data [M]⁺: 263

IR (cm⁻¹): 3320, 1650, 1420, 1200

Example 25

The reaction was conducted in the same manner as in Example 4 exceptthat 1.00 mmol of the 1-acetylamino-3-adamantanol obtained by the methodof Preparation Example 9 and 1.10 mmol of isopropenyl methacrylate wereused instead of the adamantanediol, and, as a result, a1-acetylamino-3-methacryloyloxyadamantane was obtained with a yield of99%.

Light yellow solid

Mass spectrum data [M]⁺: 277

IR (cm⁻¹): 3320, 1660, 1420, 1220

Example 26

The reaction was conducted in the same manner as in Example 2 exceptthat 1.00 mmol of the 1,3,5-adamantanetriol obtained by the method ofPreparation Example 9 and 1.10 mmol of isopropenyl acrylate were usedinstead of the adamantanediol , as a result, a1-acryloyloxy-3,5-adamantanediol was obtained with a yield of 90%.

White liquid

Mass spectrum data [M]⁺: 238

IR (cm⁻¹): 3320, 1620, 1320, 1140

Example 27

The reaction was conducted in the same manner as in Example 26 exceptthat 2.20 mmol of isopropenyl acrylate was used, and, as a result, a1,3-bis(acryloyloxy)-5-adamantanol was obtained with a yield of 85%.

White liquid

Mass spectrum data [M]⁺: 292

IR (cm⁻¹): 3300, 1610, 1310, 1150

Example 28

The reaction was conducted in the same manner as in Example 26 exceptthat 3.30 mmol of isopropenyl acrylate was used, and, as a result, a1,3,5-tris(acryloyloxy)adamantane was obtained with a yield of 95%.

White liquid

Mass spectrum data [M]⁺: 346

IR (cm⁻¹): 1620, 1320, 1140

Example 29

The reaction was conducted in the same manner as in Example 4 exceptthat 1.00 mmol of the 1,3,5-adamantanetriol obtained by the method ofPreparation Example 10 and 1.10 mmol of isopropenyl methacrylate wereused instead of the adamantanediol, and, as a result, a1-methacryloyloxy-3,5-adamantanediol was obtained with a yield of 90%.

White liquid

Mass spectrum data [M]⁺: 252

IR (cm⁻¹): 3320, 1610, 1390, 1120

Example 30

The reaction was conducted in the same manner as in Example 29 exceptthat 2.20 mmol of isopropenyl methacrylate was used, and, as a result, a1,3-bis(methacryloyloxy)-5-adamantanol was obtained with a yield of 85%.

White liquid

Mass spectrum data [M]⁺: 320

IR (cm⁻¹): 3330, 1610, 1360, 1150

Example 31

The reaction was conducted in the same manner as in Example 29 exceptthat 3.30 mmol of isopropenyl methacrylate was used, and, as a result, a1,3,5-tris (methacryloyloxy) adamantane was obtained with a yield of95%.

White liquid

Mass spectrum data [M]⁺: 388

IR (cm⁻¹): 1640, 1470, 1320, 1140

Example 32

The reaction was conducted in the same manner as in Example 2 exceptthat 1.00 mmol of the 1-nitro-3,5-adamantanediol obtained by the methodof Preparation Example 11 and 2.20 mmol of isopropenyl acrylate wereused instead of the adamantanediol, and, as a result, a1,3-bis(acryloyloxy)-5-nitroadamantane was obtained with a yield of 99%.

Light yellow solid

Mass spectrum data [M]⁺: 321

IR (cm⁻¹): 1560, 1460, 1360, 1140

Example 33

The reaction was conducted in the same manner as in Example 4 exceptthat 1.00 mmol of the 1-nitro-3,5-adamantanediol obtained by the methodof Preparation Example 11 and 2.20 mmol of isopropenyl methacrylate wereused instead of the adamantanediol, as a result, a1,3-bis(methacryloyloxy)-5-nitroadamantane was obtained with a yield of99%.

Light yellow solid

Mass spectrum data [M]⁺: 349

IR (cm⁻¹): 1570, 1440, 1360, 1120

Example 34

The reaction was conducted in the same manner as in Example 2 exceptthat 1.00 mmol of the carboxy-3,5-adamantanediol obtained by the methodof Preparation Example 11 and 2.20 mmol of isopropenyl acrylate wereused instead of the adamantanediol, and, as a result, a1,3-bis(acryloyloxy)-5-carboxyadamantane was obtained with a yield of99%.

White solid

Mass spectrum data [M]⁺: 240

IR (cm⁻¹): 3370, 1470, 1320, 1140

Example 35

The reaction was conducted in the same manner as in Example 4 exceptthat 1.00 mmol of the 1-carboxy-3,5-adamantanediol obtained by themethod of Preparation Example 12 and 2.20 mmol of isopropenylmethacrylate were used instead of the adamantanediol, and, as a result,a 1,3-bis(methacryloyloxy)-5-carboxyadamantane was obtained with a yieldof 99%.

White solid

Mass spectrum data [M]⁺: 268

IR (cm⁻¹): 3350, 1450, 1320, 1130

Example 36

(1) The oxidization in an oxygen atmosphere was conducted in the samemanner as in Preparation Example 1 except that 1,3-dicarboxyadamantanewas used instead of the adamantane and, as a result, a1,3-dicarboxy-5-adamantanol (yield: 35%, white solid) and a1,3-dicarboxy-5,7-dihydroxyadamantane (yield: 37%, white solid) wereobtained with a conversion of 91%.

(2) To 2 mL of dioxane were added 1.00 mmol of1,3-dicarboxy-5-adamantanol, 0.10 mmol of samarium iodide (SmI₂), 2.20mmol of isopropenyl acrylate, and the resultant mixture was stirred at atemperature of 50° C. for 4 hours. The analysis by gas chromatographyshowed the formation of a 1,3-dicarboxy-5-acryloyloxyadamantane (yield:82%, white solid) in the reaction mixture.

Mass spectrum data [M]⁺: 294, [M]⁻: 223, [M]⁻⁻: 178, [M]⁻⁻⁻: 133

(3) The reaction was conducted in the same manner as said (2) exceptthat 1,3-dicarboxy-5,7-dihydroxyadamantane was used instead of the1,3-dicarboxy-5-adamantanol, and, as a result, a1,3-dicarboxy-5-acryloyloxy-7-adamantanol (yield: 86%, white solid) wasobtained.

Mass spectrum data [M]⁺: 310, [M]⁻: 292, [M]⁻⁻: 221, [M]⁻⁻⁻: 176

Example 37

(1) The oxidization under an oxygen atmosphere was conducted in the samemanner as in Preparation Example 1 except that 1,3-tricarboxyadamantanewas used instead of the adamantane, and, as a result, a1,3,5-tricarboxy-7-adamantanol (yield: 57%, white solid) was obtainedwith a conversion of 62%. The 1,3,5-tricarboxyadamantane was obtained inthe same manner as in Preparation Example 5 except that the reactiontime was 12 hours and the temperature was 80° C.

(2) The reaction was conducted in the same manner as the step of Example36 (2) except that 1,3,5-tricarboxy-7-adamantanol was used instead ofthe 1,3-dicarboxy-5-adamantanol, and, as a result, a1,3,5-tricarboxy-7-acryloiloxyadamantane (yield: 76%, white solid) wasobtained.

Mass spectrum data [M]⁺: 338, [M]⁻: 267, [M]⁻⁻: 222, [M]⁻⁻⁻: 177

Example 38

(1) The oxidization in an oxygen atmosphere was conducted in the samemanner as in Preparation Example 1 except that 1-carboxyadamantane wasused instead of the adamantane, and as a result, a1-carboxy-3,5-dihydroxyadamantane (yield: 44%, white solid) and a1-carboxy-3,5,7-trihydroxyadamantane (yield: 34%, white solid) wereobtained with a conversion of 98%.

(2) The reaction was conducted in the same manner as the step of Example36 (2) except that 1-carboxy-3,5-dihydroxyadamantane was used instead ofthe 1,3-dicarboxy-5-adamantanol, and, as a result, a1-carboxy-3-hydroxy-5-acryloyloxyadamantane (yield: 84%, white solid)was obtained.

Mass spectrum data [M]⁺: 266, [M]⁻: 248, [M]⁻⁻: 177, [M]⁻⁻⁻: 132

(3) The reaction was conducted in the same manner as said (2) exceptthat 1-carboxy-3,5,7-trihydroxyadamantane was used instead of the1-carboxy-3,5-dihydroxyadamantane, and, as a result, a1-carboxy-3,5-dihydroxy-7-acryloyloxyadamantane (yield: 81%, whitesolid) was produced.

Mass spectrum data [M]^(+: 282,) [M]⁻: 264, [M]⁻⁻: 246, [M]⁻⁻: 175

Example 39

(1) The oxidization in an oxygen atmosphere was conducted in the samemanner as in Preparation Example 1 except that1,3,5-trihydroxyadamantane was used instead of the adamantane ofPreparation Example 1, and, as a result, a 1,3,5,7-tetrahydroxyadamantne(yield: 62%) with a conversion of 87%.

(2) The reaction was conducted in the same manner as the step of Example36 (2) except that 1,3,5,7-tetrahydroxyadamantane was used instead ofthe 1,3-dicarboxy-5-adamantanol, and, as a result, a1,3,5-trihydroxy-7-acryloyloxyadamantane (yield: 83%, white solid) wasobtained.

Mass spectrum data [M]⁺: 254, [M]⁻: 236, [M]⁻⁻: 218, [M]⁻⁻⁻: 200

Example 40

(1) The oxidization in an oxygen atmosphere was conducted in the samemanner as in Preparation Example 1 except that 1-acetyladamantane wasused instead of the adamantane, and, as a result, a1-acetyl-3-hydroxyadamantane (yield: 46%, white solid) and a1-acetyl-3,5-dihydroxyadamantane (yield: 33%, white solid) were obtainedwith a conversion of 98%.

(2) The reaction was conducted in the same manner as the step of Example36 (2) except that 1-acetyl-3-hydroxyadamantane was used instead of the1,3-dicarboxy-5-adamantanol, and, as a result, a1-acety-3-acryloyloxyadamantane (yield: 97%, white solid) was obtained.

Mass spectrum data [M]⁺: 248, [M]⁻: 177, [M]⁻⁻: 162, [M]⁻⁻⁻: 133

(3) The reaction was conducted in the same manner as said (2) exceptthat 1-acetyl-3,5-dihyroxyadamantane was used instead of the1-acetyl-3-hydroxyadamantane, and, as a result, a1-acetyl-3-hydroxy-5-acryloyloxyadamantane (yield: 84%, white solid) wasobtained.

Mass spectrum data [M]⁺: 264, [M]⁻: 246, [M]⁻⁻: 175, [M]⁻⁻⁻: 160

Example 41

(1) The oxidization in an oxygen atmosphere was conducted in the samemanner as in Preparation Example 1 except that 2-oxoadamantane (whitesolid) was used instead of the adamantane, and, as a result, a1-hydroxyadamantane-2-one (yield: 36%, white solid), a1-hydroxyadamantane-4-one (yield: 30%, white solid) and a1,3-dihydroxyadamantane-4-one (yield: 22%, white solid) were obtainedwith a conversion of 94%.

(2) The reaction was conducted in the same manner as the step of Example36 (2) except that 1-hydroxyadamantane-2-one was used instead of the1,3-dicarboxy-5-adamantanol, and, as a result, a1-acryloyloxyadamantane-2-one (yield: 94%, white solid) was obtained.

Mass spectrum data [M]⁺: 220, [M]⁻: 149

(3) The reaction was conducted in the same manner as said (2) exceptthat 1-hydroxyadamantane-4-one was used instead of the1-hydroxyadamantane-2-one, and, as a result, a1-acryloyloxyadamantane-4-one (yield: 95%, white solid) was obtained.

Mass spectrum data (M]⁺: 220, [M]⁻: 149

(4) The reaction was conducted in the same manner as said (2) exceptthat 1,3-dihydroxyadamantane-4-one was used instead of the1-hydroxyadamantane-2-one, and, as a result, a1-acryloyloxy-3-hydroxyadamantane-4-one (yield: 87%, white solid) wasproduced.

Mass spectrum data [M]⁺: 236, [M]⁻: 218, [M]⁻⁻: 147

Example 42

(1) The oxidization in an oxygen atmosphere was conducted in the samemanner as in Preparation Example 1 except that 1,3-dimethyladamantanewas used instead of the adamantane, and, as a result, a1,3-dimethyl-5,7-dihydroxyadamantane (yield: 44%, white solid) and a1,3-dimethyl-5-hydroxyadamantane (yield: 34%, white solid) were obtainedwith a conversion of 99%.

(2) The reaction was conducted in the same manner as the step of Example36 (2) except that 1,3-dimethyl-5,7-dihydroxyadamantane was used insteadof the 1,3-dicarboxy-5-adamantanol, and, as a result, a1,3-dimethyl-5-hydroxy-7-acryloyloxyadamantane (yield: 87%, white solid)was obtained.

Mass spectrum data [M]⁺: 250, [M]⁻: 232, [M]⁻⁻: 161, [M]⁻⁻⁻: 146

(3) The reaction was conducted in the same manner as said (2) exceptthat 1,3-dimethyl-5-hydroxyadamantane was used instead of the1,3-dimethyl-5,7-dihydroxyadamantane, and, as a result, a1,3-dimethyl-5-acryloyloxyadamantane (yield: 96%, colorless liquid) wasproduced.

Mass spectrum data [M]⁺: 234, [M]⁻: 163, [M]⁻⁻: 148, [M]⁻⁻⁻: 133

Example 43

(1) The oxidization in an oxygen atmosphere was conducted in the samemanner as in Preparation Example 1 except that1-methoxycarbonyladamantane was used instead of the adamantane, and, asa result, a 1-methoxycarbonyl-3-hydroxyadamantane (yield: 42%) and a1-methoxycarbonyl-3,5-hydroxyadamantane (yield : 33%) were obtained witha conversion of 91%.

(2) The reaction was conducted in the same manner as the step of Example36 (2) except that 1-methoxycarbonyl-3-hydroxyadamantane was usedinstead of the 1,3-dicarboxy-5-adamantanol, and, as a result, a1-methoxycarbonyl-3-acryloyloxyadamantane (yield: 87%, white solid) wasobtained.

Mass spectrum data [M]⁺: 267, [M]⁻: 193, [M]⁻⁻: 148

(3) The reaction was conducted in the same manner as said (2) exceptthat 1-methoxycarbonyl-3,5-hydroxyadamantane was used instead of the1-methoxycarbonyl-3-hydroxyadamantane, and, as a result, a1-methoxycarbonyl-3-hydroxy-5-acryloyloxyadamantane (yield: 84%, whitesolid) was produced.

Mass spectrum data [M]⁺: 280, [M]⁻: 262, [M]⁻⁻: 191, [m]⁻⁻⁻: 146

What is claimed is:
 1. A process for producing a polymerizableadamantane derivative shown by the following formula (1):

wherein R¹, R², R³ and R⁴ independently represent at least onesubstituent selected from a non-reactive atom, a non-reactive group, anda polymerizable unsaturated group, and at least one member selected fromR¹, R², R³ and R⁴ is a polymerizable unsaturated group; X represents aconnecting group comprising an ester group or an amide group, n denotes0 or 1, and X may be different from each other according to R¹, R², R³and R⁴, with the proviso that n is 0 when R¹, R², R³ or R⁴ is anon-reactive atom and a non-reactive group, and the binary carbon atomconstituting the adamantane skeleton may have an oxo group; whichcomprises subjecting a compound shown by the following formula (1a):

wherein R^(1a), R^(2a), R^(3a) and R^(4a) independently represent atleast one substituent selected from a non-reactive atom, a non-reactivegroup, a hydroxyl group, a hydroxymethyl group, a carboxyl group, anamino group and a reactive group derived therefrom, and at least onemember selected from R^(1a), R^(2a), R^(3a) and R^(4a) is a hydroxylgroup, a hydroxymethyl group, a carboxyl group, an amino group or areactive group derived therefrom, and the binary carbon atomconstituting the adamantane skeleton may have an oxo group; and at leastone compound selected from an alcohol having a polymerizable unsaturatedbond, a carboxylic acid having a polymerizable unsaturated bond, anamine having a polymerizable unsaturated bond and a reactive derivativethereof to an esterification reaction or amidation reaction in thepresence of a catalyst comprising a compound containing a Group 3Aelement of the Periodic Table of Elements.
 2. A process for producing apolymerizable adamantane derivative according to claim 1, wherein saidpolymerizable unsaturated group has at least one polymerizableunsaturated double bond selected from vinyl group, isopropenyl group andallyl group.
 3. A process for producing a polymerizable adamantanederivative according to claim 1, wherein said X denotes an ester bondand at least one group selected from R¹, R², R³ and R⁴ has a vinyl groupor an isopropenyl group.
 4. A process for producing a polymerizableadamantane derivative according to claim 1, wherein said adamantanederivative in which at least one group selected from R^(1a), R^(2a),R^(3a) and R^(4a) is a hydroxyl group or a reactive group derivedtherefrom is subjected to an esterification reaction with acrylic acid,methacrylic acid and a derivative thereof.
 5. A process for producing apolymerizable adamantane derivative according to claim 1, wherein saidcompound containing a Group 3A element of the Periodic Table of Elementscomprises a compound containing a rare earth element.
 6. A process forproducing a polymerizable adamantane derivative according to claim 5,wherein said compound containing a rare earth element is at least onemember selected from a scandium compound, a lanthanum compound anytterbium compound, a gadolinium compound and a samarium compound.
 7. Aprocess for producing a polymerizable adamantane derivative according toclaim 5, wherein said compound containing a rare earth element is a di-or trivalent samarium compound.
 8. A process for producing apolymerizable adamantane derivative according to claim 1, wherein saidcarboxylic acid having a polymerizable unsaturated bond, and saidreactive derivative thereof is at least one member selected from thegroup consisting of an organic carboxylic acid having anα,β-ethylenically unsaturated double bond or triple bond or an acidhalide thereof, a lower Cl₁₋₄alkyl ester of an organic carboxylic acidand a C₂₋₄alkenyl ester of an organic carboxylic acid.
 9. A process forproducing a polymerizable adamantane derivative according to claim 1,wherein said adamantane having 1 to 4 of hydroxyl group in the molecule,is allowed to react in the presence of a compound containing a rareearth element with at least one compound selected from the groupconsisting of an organic carboxylic acid having an α,β-ethylenicallyunsaturated double bond or an acid halide thereof, a C₁₋₄ lower alkylester of an organic carboxylic acid and a C₂₋₄ lower alkenyl ester of anorganic carboxylic acid.
 10. A process for producing a polymerizableadamantane derivative according to claim 1, which comprises subjectingsaid adamantane derivative to at least one step among the followingoxidation step (i), carboxylation step (ii), and nitration step (iii):(i) an oxidation step using oxygen in the presence of a catalystcomprising an imide compound shown by the following formula (2):

wherein R¹¹ and R¹² are the same or different, each representing ahydrogen atom, a halogen atom, an alkyl group, an aryl group, acycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group,an alkoxycarbonyl group or an acyl group; R¹¹ and R¹² may bond togetherto form a double bond, an aromatic or non-aromatic ring; Y represents anoxygen atom or a hydroxyl group; and m denotes an integer of 1 to 3;(ii) a carboxylation step using carbon monoxide and oxygen in thepresence of the catalyst comprising the imide compound shown by theformula (2); (iii) at least one nitration step among the following(iiia), (iiib), and (iiic): (iiia) a nitration step using a nitrogenoxide in the presence of the catalyst comprising the imide compoundshown by the formula (2); (iiib) a nitration step using at least onenitrogen oxide selected from dinitrogen oxide and nitrogen monoxide withoxygen; and (iiic) a nitration step using nitrogen dioxide; to form acompound to which at least one reactive group selected from hydroxylgroup, carboxyl group, and nitro group is introduced and subjecting thecompound to said esterification or amidation reaction; wherein theadamantane derivative is represented by said formula (1a), R^(1a),R^(2a), R^(3a) and R^(4a) therein may be the same or differentlyhydrogen atoms, non-reactive atoms, and non-reactive groups and at leastone member among R^(1a), R^(2a), R^(3a) and R^(4a) is a hydrogen atom.11. A process for producing a polymerizable adamantane derivativeaccording to claim 10, wherein after at least one step of saidcarboxylation step (ii) and nitration step (iii), a reaction product isfurther subjected to a reduction step to form at least one groupselected from a hydroxymethyl group and an amino group.
 12. A processfor producing a polymerizable adamantane derivative according to claim10, wherein said catalyst comprises the imide compound shown by theformula (2) and a co-catalyst.
 13. A process for producing apolymerizable adamantane derivative according to claim 12, wherein saidco-catalyst is a compound containing at least one element selected fromthe group consisting of Group 3A elements, Group 4A elements, Group 5Aelements, Group 6A elements, Group 7A elements, Group 8 elements andGroup 1B elements of the Periodic Table of Elements.
 14. A polymerizableadamantane derivative shown by the following formula:

wherein R¹, R², R³ and R⁴ may be the same or different each representingat least one substituent selected from a non-reactive atom, a non-reactive group, and a polymerizable unsaturated group, and at least oneselected from R¹, R², R³ and R⁴ is a polymerizable unsaturated group; Xdenotes a —OC(═O)—group in which the left end thereof is intended as amoiety bound to an adamantane back bone; n denotes 0 or 1 with theproviso that n is 0 when R¹, R², R³ or R⁴ is a non-reactive atom or anon-reactive group; and at least one member selected from R¹, R², R³ andR⁴ is a non-reactive group selected from the group consisting of nitrogroup, amino group which may be protected by a protective group or anN-substituted amino group which may be protected by a protective group,carboxyl group which may be protected by a protective group andhydroxymethyl group which may be protected by a protective group, andthe binary carbon atom constituting the adamantane skeleton may have anoxo group.